CN110002840A - A method of automatic humidifying material is prepared using calcium chloride - Google Patents

A method of automatic humidifying material is prepared using calcium chloride Download PDF

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Publication number
CN110002840A
CN110002840A CN201910225619.5A CN201910225619A CN110002840A CN 110002840 A CN110002840 A CN 110002840A CN 201910225619 A CN201910225619 A CN 201910225619A CN 110002840 A CN110002840 A CN 110002840A
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calcium chloride
cullet
lime stone
humidity
automatic humidifying
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CN110002840B (en
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景镇子
裘鹏程
祁郁捷
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Tongji University
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Drying Of Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of methods for preparing automatic humidifying material using calcium chloride, belong to Indoor environment functionality finishing material preparation technical field.First cullet and lime stone are crushed, sieves with 100 mesh sieve and dries；Cullet is measured first with mass percent again: lime stone=20%~90%:10%~80%, cullet and lime stone are measured again: calcium chloride=85%~99%:1%~15%, 5%~10% water or sodium hydroxide solution of cullet and lime stone and calcium chloride total weight are finally measured, the concentration of sodium hydroxide solution is 2~5mol/L；After mixing by each raw material, it is pressed into bulk sample under the briquetting pressure of 10~30MPa and demoulds, at 140 DEG C~200 DEG C, progress hydrothermal hardening 1~for 24 hours, it is high intensity automatic humidifying construction material that blocky cured article is made after drying.Present invention process is simple, energy conservation and environmental protection, and obtained product has superior moisture absorption and desorption property, the requirement of far super national standard " JC/T 2082-2011 humidity conditioning function interior architecture ornament materials ".

Description

A method of automatic humidifying material is prepared using calcium chloride
Technical field
The present invention relates to a kind of methods for preparing automatic humidifying material using calcium chloride, belong to Indoor environment functionality decorations Face technical field of material.
Background technique
With the development of the times with the promotion of living standard, requirement of the people for amenity be higher and higher.And The time for averagely having nearly 90% in life of people is to spend indoors, therefore, the comfort of living environment and health further by Pay attention to.Wherein, other than temperature, indoor humidity suffers from great influence to the health of people, comfort level etc.. And humidity is influenced by relative air humidity.When relative humidity is excessive, body-sensing is sultry, and thin in air Bacterium, virus breeding speed are fast；When relative air humidity is too small, human body just may feel that dry and uncomfortable.Studies have shown that Interior Space It is than convenient that gas relative humidity (RH), which is 40%~70%,.And automatic humidifying material is not necessarily to additional condition, so that it may realize Indoor humidity is automatically maintained within the scope of this.
Automatic humidifying material is proposed that it can rely on the absorb-discharge humid of itself by the western rattan of Japanese scholars, palace open country et al. earliest Can, relative air humidity is automatically adjusted, improves indoor residence comfort, and can save using energy consumption used in air conditioner dehumidification.Material The humidity of material is mainly determined by the diffusion of duct (or stratiform) structure and water vapour molecule in hole.When in air Steam partial pressure is higher than in duct on concave meniscus when the saturated vapor pressure of water, and vapor is just adsorbed；Conversely, being just desorbed.This Outside, the relational graph of the humidity and aperture established according to scholars such as new wells: the corresponding aperture RH=40% is 3.2nm, RH= 70% corresponding aperture be 7.4nm, if in material rich in 3.2~7.4nm it is mesoporous when, the material can make indoor humidity from It moves in the range of maintaining this human body the most comfortable of 40%-70%, i.e., when indoor humidity is higher than 70%, material can be inhaled automatically It is wet, reduce indoor humidity；When indoor humidity be lower than 40%, material can automatic moisture releasing, improve indoor humidity.
Currently, all prepare humidity adjusting material using inorganic mineral, it is all to directly adopt that there are a large amount of mesoporous, specific surface areas Greatly, the strong mineral of adsorption capacity are raw material, such as sepiolite (looking at Patent No. ZL201510017134.9 patent), diatomite (patent for looking at Patent No. CN108262003A).The patent of above-mentioned Patent No. CN108262003A is to utilize diatomite system Standby diatom base hydration calcium silicate powder humidity adjusting material, but because it does not have intensity, cannot individually be used directly for building Metope can only add part, affect automatic humidifying effect.The standby damping of the patent system of Patent No. ZL201510017134.9 It is raw material that material, which all directlys adopt the superior sepiolite of meso-hole structure,.
Summary of the invention
The object of the present invention is to provide a kind of simple process, it is low in cost, directly as Indoor environment functionality facing The preparation method of the automatic humidifying material of material.
In order to achieve the above object, the present invention find after study calcium chloride because of its distinctive deliquescence water absorbing properties, by with In producing all kinds of desiccant, if the patent of Patent No. CN102211016A is using active carbon particle or activated carbon fibre as base Bottom adds a certain amount of calcium chloride and moisture-absorbing desiccant is made.But its only adsorbable water, can not but release desorption water, so cannot be into Row humidity regulation.For this purpose, calcium chloride is also applied to humidity adjusting material not on building materials market at present.
Amount of the cullet in China is very big.Lime stone accounts for the 1/20, Zhan Quan of national territorial area in the reserves very abundant in China 60% or more of ball itself is also a kind of common raw material of building materials.Cullet and lime stone are because its meso-hole structure is poor, mesh It is preceding to be directly used in the case for preparing humidity adjusting material not yet.
The present invention is added calcium chloride, passes through hydrothermal hardening mode using the lime stone of pore structure difference and cullet as raw material Tobermorite is generated, and the distinctive microcellular structure of tobermorite improves product humidity.Side of the present invention Method makes full use of calcium chloride is distinctive to deliquesce water absorbing properties and improved meso-hole structure, greatly improves product humidity, And lower reaction temperature, the more meso-hole structures that can be generated in retained product while reducing production energy consumption further increase Product humidity.Subsequent process test obtains the material, and water absorption rate can reach 312g/m for 24 hours2, far super national standard, with excellent Automatic humidifying performance more.
Specific step is as follows:
First cullet and lime stone are crushed, sieves with 100 mesh sieve and dries respectively；Useless glass is first measured with mass percent again Glass: lime stone=20%~90%:10%~80%, then measure cullet and lime stone: calcium chloride=85%~99%:1% ~15%, finally measure 5%~10% water or sodium hydroxide solution of cullet and lime stone and calcium chloride total weight, hydrogen-oxygen The concentration for changing sodium solution is 2~5mol/L, after mixing by each raw material of above-mentioned measurement, in the briquetting pressure of 10~30MPa Under be pressed into bulk sample and demould, under the conditions of 140 DEG C~200 DEG C, carry out hydrothermal hardening 1~for 24 hours, be made after drying Blocky cured article is high-intensitive automatic humidifying construction material.After testing, which has compared with high breaking strength and has 3 in remote super national standard " JC/T 2082-2011 humidity conditioning function interior architecture ornament materials "~requirements of hygroscopic capacities at different levels for 24 hours, And the respective specified of moisture releasing amount, it can satisfy the requirement of interior architecture decorative material.
Advantages of the present invention and effect are:
1, due to the addition of calcium chloride of the present invention, the distinctive deliquescence water absorbing properties of calcium chloride can be made full use of, enhancing is inhaled Wet effect, and synthesize to obtain the tobermorite with certain meso-hole structure by hydro-thermal reaction, it not only can be further Improve product meso-hole structure, greatly improve the mesoporous content of 3.2~7.4nm in product, avoid calcium chloride only adsorbable water, But the defect of desorption water can not be released, so that product has the performance of superior automatic adjustment humidity.
2, due to hydrothermal hardening technique of the present invention, reaction temperature is lower than 200 DEG C, on the one hand, low energy consumption, with biography System burning process temperature is higher than 1000 DEG C and compares, and production energy consumption reduces by 5 times, and product preparation cost is low；On the other hand lower temperature Degree is conducive to the reservation of the meso-hole structure generated in product, is conducive to the raising of humidity.
3, the present invention not only has certain flexural strength (>=12MPa), but also 24 hours water absorption rate >=125g/m2, remote high In national standard and domestic similar product, water absorption rate highest can surpass up to 312g/m within 24 hours2, and have desorption curvature it is found that its Moisture releasing speed is fast, moisture releasing ability is strong, has brilliant responsiveness.
4, the present invention is poor by equal pore structure, it is difficult to which the lime stone and cullet for synthesizing automatic humidifying material are prepared into certainly Dynamic humidity adjusting material, enables China's lime stone mineral products abundant and cullet cycling and reutilization, and is directly solidified into certainly Indoor wall nogging, the ceiling etc. for moving humidity conditioning function, can improve residence comfort well, avoid the bad body such as sultry, dry Sense, Social benefit and economic benefit are fairly obvious.
Detailed description of the invention
Fig. 1 is the humidity response curve of the solidified body product of different calcium chloride contents in the embodiment of the present invention 1.
Fig. 2 is the flexural strength variation diagram of the solidified body product of different calcium chloride contents in the embodiment of the present invention 1.
Fig. 3 is the porosity distribution figure of the solidified body product of different calcium chloride contents in the embodiment of the present invention 2.
Fig. 4 is the XRD spectrum of addition calcium chloride and the solidified body product for being not added with calcium chloride in the embodiment of the present invention 2.
Fig. 5 is the SEM photograph that the solidified body product after calcium chloride is added in the embodiment of the present invention 2.
Fig. 6 is the humidity response curve of different cullet and the solidified body product of lime stone ratio in the embodiment of the present invention 3.
Specific embodiment
Embodiment 1
Selection sieves with 100 mesh sieve and the cullet and limestone mix dried indicate (wherein cullet and lime stone with cg Mass percent is 50%:50%).
The embodiment 1 probes into different calcium chloride contents to solidified body product humidity using calcium chloride content as variable It influences, and is analyzed.Appropriate calcium chloride (1%~15%) is added in cg first, then additionally measure total weight 5%~ 10% water or sodium hydroxide solution (concentration is 2~5mol/L), after mixing by each raw material according to the above ratio, in FW-4 type Compression moulding (briquetting pressure 30MPa) under desk type powder tablet press machine, it is solid that the sample after demoulding is put into progress hydro-thermal in water heating kettle Change (200 DEG C of temperature, time 15h).Sample (40mm × 15mm × 6mm) after solidification is dried in 80 DEG C of baking ovens to be obtained afterwards for 24 hours Solidified body product.
Solidified body product (sample) is put into the environment of relative humidity (RH) 33% for 24 hours, it is allowed to reach adsorption equilibrium.
Relative humidity (RH) NaCl saturated solution for being 75% is put into closed box, constant temperature and humidity box temperature is then set Degree is 25 DEG C, and relative humidity (RH) is 75%.When the temperature and humidity in climatic chamber is kept at 25 DEG C and 75% When, and temperature and humidity variation be no more than ± 0.1 when, assert closed box in temperature and humidity keep stablize.
It sets the every 10min of balance and measures the quality of a sample, and measurement data is automatically entered into computer.
It is up to the sample that adsorption equilibrium is handled well to be put into rapidly in the pallet of the specimen holder in closed box, then electronics Balance is reset, and simultaneously closes off closed box and climatic chamber, and material carries out moisture absorption, and the variation of balance numerical value at this time is that material is inhaled Receive the variation of biodiversity.The sucting wet experiment period is for 24 hours, after data are write all over for 24 hours, then saturated solution in humidity response experiment Change MgCl into2·6H2O solution, and climatic chamber temperature is set as 25 DEG C, relative humidity (RH) is 75%, to control closed RH in case continues the mass change for recording sample, is at this time moisture releasing process 33%, and the moisture releasing time is equally for 24 hours.Thus It can be concluded that moisture adsorption and releasing amount of the sample in humidity variation circulation be with the curve of time change, i.e. humidity response curve, As shown in Figure 1.As shown in Figure 1, when ambient humidity be higher than 70% when, material can the automatic moisture absorption from environment, make under ambient humidity Drop；When ambient humidity be lower than 40% when, material can the automatic moisture releasing into environment, improve ambient humidity, thus reach one from The effect of dynamic regulating environmental humidity, can improve residence comfort well, avoid the bad body-sensing such as sultry, dry.According to industry Standard " JC-T 2082-2011 debugging function interior architecture ornament materials ", product thickness produced by the present invention belongs to greater than 3mm Third class, the specific humidity index measured and the table seen below with national standard comparison.
By table above it is found that national standard cannot be reached by not adding the solidified body of calcium chloride, after adding appropriate calcium chloride Product humidity greatly improves: the product of 3%, 5% and 10% calcium chloride of addition is not respectively than adding the product of calcium chloride for 24 hours Water absorption has more 223%, 474% and 721% respectively, is higher by 105%, 263% and 420% respectively compared with national standard.In addition, addition Moisture releasing rate (85%) is higher than 75% to the product of 3% calcium chloride for 24 hours, though and add the product moisture releasing rate for 24 hours of 5% and 10% calcium chloride It is low less than 75%, but its moisture releasing amount is respectively 131g/m for 24 hours2And 189g/m2, moisture releasing amount unit is all larger than 20g/m2, meet national standard It is required that.
As can be seen from FIG. 2, as calcium chloride content is continuously improved, flexural strength is declined, but adds 10% calcium chloride Product flexural strength still have 12MPa (compression strength 60Mpa) or more, meet corresponding industry requirement.Comprehensively consider addition 10% When calcium chloride, product humidity is very superior, therefore does not continue to addition calcium chloride, and selected 10% calcium chloride is for this The optimum value of column embodiment.
Embodiment 2
It using the content of calcium chloride as variable, observes it and changes the influence for humidity, inquire into calcium chloride for automatic The effect of humidity adjusting material.
International Union of Chemistry (IUPAC) adsorption isothermal curve type divided is divided according to crossing material letter and controlling etc. Analysis, the material for being found to have IV type adsorption isothermal curve are relatively suitable as humidity adjusting material；And it can with Kelvin and correlation formula Material of the aperture between 3.2~7.4nm is released, indoor relative humidity can be made to be automatically maintained at 40%~70% this human body most Comfortable range.
Solidified body product (sample) is made using embodiment 1.Experimental result is as in Figure 3-5, from Fig. 3 it can be found that true Above-mentioned theory is better conformed in fact, as calcium chloride content is continuously improved, mesoporous content is constantly promoted, especially 3~7.4nm The mesoporous content in aperture greatly improves, this is the main reason for product humidity improves.
In conjunction with Fig. 4, it can be found that the peak in XRD spectrum near 2 θ=30 ° disappears, near 2 θ=7 ° after addition calcium chloride Peak enhancing, so that explanation can promote original flocks shape C-S-H gel further occurrence to react after calcium chloride is added, turn Become tobermorite, and can be found that product tobermorite rich in mesoporous by Fig. 5.And lower reaction temperature (≤ 200 DEG C) there is reservation using meso-hole structure, greatly improve the aperture 3.2~7.4nm content, the result phase of this and Fig. 3 It coincide.As a result, this examples of series it can be concluded that, with the increase of calcium chloride content, original flocks shape C-S-H gel conversion is Tobermorite rich in meso-hole structure, so that aperture refines, it is the main reason for sample humidity greatly improves.
On the other hand, due to calcium chloride have the function of deliquesce moisture absorption, when it is distributed in it is mesoporous middle when, since it has attraction The trend of hydrone reduces needed for absorption so that being easier adsorbed water molecule compared to the product of no addition calcium chloride Energy enables product to adsorb more hydrones, greatly improves product automatic humidifying performance.
In summary reason, by embodiment 2, we it can be concluded that, the addition of calcium chloride, on the one hand, improve mesoporous knot Structure, and the mesoporous content of 3.2~7.4nm in product is significantly increased；On the other hand, because with its distinctive deliquescence water absorbing properties, The moisture pick-up properties of product can be greatly improved.This is the cardinal principle that this product realizes automatic humidifying function.
Embodiment 3
It is 10% constant that the embodiment, which selectes calcium chloride content, using the mass ratio of cullet and lime stone as variable, is probed into Influence of the different calcium chloride contents to solidified sample humidity, and analyzed.
The mixture cg for configuring different cullet Yu lime stone mass ratio (2:8~6:4) first, is converted into mass percent For cullet: lime stone=20%~60%:40%~80%.Then with calcium chloride: cg=1:9 is mixed, then additional quantity 5%~10% water or sodium hydroxide solution (concentration is 2~5mol/L) for taking total weight, according to the above ratio mix each raw material After uniformly, the compression moulding (briquetting pressure 30MPa) under FW-4 type desk type powder tablet press machine, the sample after demoulding is put into hydro-thermal Hydrothermal hardening (200 DEG C of temperature, time 15h) are carried out in kettle.Sample (40mm × 15mm × 6mm) after solidification is in 80 DEG C of baking ovens After drying for 24 hours, the test of humidity response curve is carried out, test results are shown in figure 6.
It will be appreciated from fig. 6 that the humidity of product greatly improves as cullet and lime stone mass ratio improve, work as quality Than being that humidity is best for 1:1, up to 312g/m2.When continuing to increase quality ratio, humidity is declined, this is main It is to be determined by the content and growing state of tobermorite, at the beginning, as mass ratio increases, the content of tobermorite is big Width improves, and its distinctive meso-hole structure is advantageous to the raising of humidity；But when mass ratio is excessively high, tobermorite Undue growth, meso-hole structure are gradually destroyed, and humidity is also greatly reduced.Therefore, it selectes cullet and lime stone is 1:1 For the optimum value of the series embodiment.
Equipment needed for the above sample test humidity response curve are as follows: climatic chamber: model JYM-103B, in manufacturer Hai Jiayu scientific instrument Co., Ltd, adjusting humidity range RH25-95% ± 1%RH, ± 0.2 DEG C of -15-85 DEG C of temperature；Electricity Sub- assay balance: model Shimadzu AUW220, Shanghai sage section, manufacturer experimental instruments and equipment limited, relevant parameter 220g, 0.1mg；Temperature and humidity recorder: model 179A-TH, Ai Purui precision Photoelectric Co., Ltd., manufacturer, test scope humidity 0- 100%RH ± 1.8%RH, ± 0.2 DEG C of -40-100 DEG C of temperature；Make closed box: 30cm × 25cm × 22cm by oneself；Electronic computer: Model: HSTNC-002L-TC, the production of computer Co., Ltd, Hewlett-Packard.

Claims (2)

1. a kind of method for preparing automatic humidifying material using calcium chloride, its feature is as follows:
First cullet and lime stone are crushed, sieves with 100 mesh sieve and dries respectively；Cullet is measured first with mass percent again: stone Lime stone=20%~90%:10%~80%, then measure cullet and lime stone: calcium chloride=85%~99%:1%~ 15%, finally measure 5%~10% water or sodium hydroxide solution of cullet and lime stone and calcium chloride total weight, hydroxide The concentration of sodium solution is 2~5mol/L；After mixing by each raw material of above-mentioned measurement, under the briquetting pressure of 10~30MPa It is pressed into bulk sample and demoulds, under the conditions of 140 DEG C~200 DEG C, progress hydrothermal hardening 1~for 24 hours, block is made after drying Shape cured article is high-intensitive automatic humidifying construction material.
2. a kind of method for preparing automatic humidifying material using calcium chloride according to claim 1, its feature is as follows: described High-intensitive automatic humidifying construction material be directly to be solidified into indoor wall nogging, ceiling with automatic humidifying function, pass through Detection, product is with compared with high breaking strength and with remote super national standard " JC/T2082-2011 humidity conditioning function interior architecture decoration material Material " in the 3~respective specified of the requirement of hygroscopic capacities at different levels and moisture releasing amount for 24 hours, meet making for interior architecture decorative material With requiring.
CN201910225619.5A 2019-03-25 2019-03-25 Method for preparing automatic humidity adjusting material by using calcium chloride Active CN110002840B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110482975A (en) * 2019-09-02 2019-11-22 同济大学 A kind of preparation method of light-high-strength humidity adjusting material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106927737A (en) * 2017-03-06 2017-07-07 同济大学 A kind of preparation method of lime ground mass high-intensity building materials
CN108046738A (en) * 2017-12-08 2018-05-18 上海海顾新材料科技有限公司 A kind of low-temperature setting sea sand is the method for intelligent damping construction material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106927737A (en) * 2017-03-06 2017-07-07 同济大学 A kind of preparation method of lime ground mass high-intensity building materials
CN108046738A (en) * 2017-12-08 2018-05-18 上海海顾新材料科技有限公司 A kind of low-temperature setting sea sand is the method for intelligent damping construction material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110482975A (en) * 2019-09-02 2019-11-22 同济大学 A kind of preparation method of light-high-strength humidity adjusting material

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