CN106660880A - Calcium-cellulose organo-mineral complex, preparation process and applications - Google Patents
Calcium-cellulose organo-mineral complex, preparation process and applications Download PDFInfo
- Publication number
- CN106660880A CN106660880A CN201480080895.2A CN201480080895A CN106660880A CN 106660880 A CN106660880 A CN 106660880A CN 201480080895 A CN201480080895 A CN 201480080895A CN 106660880 A CN106660880 A CN 106660880A
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- CN
- China
- Prior art keywords
- cellulose
- calcium
- complex compound
- paste
- quick lime
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a calcium-cellulose organo-mineral complex capable of being obtained by reaction of quicklime over cellulose, in aqueous suspension, to the method of obtaining same and to the applications thereof.
Description
The present invention relates to a kind of organic-mineral complex compound, it can be obtained by the chemical degradation of cellulose, be related to life
Method and the application of the latter of such complex compound are produced, particularly for building field.
Cellulose, it is organic polymer most abundant in biosphere, is that one kind is bonded in one by by β (1-4) keys
Rise glucose unit constitute polysaccharide, and its number can be up to it is thousands of.It is a kind of linear polymer, its sequence
Secondary structure is provided for, the structure can be similar to by the cellobiose dimerization unit in spirochetal each corner
The conveyor screw of composition, and its tertiary structure is the beam of polysaccharide chain arranged parallel to each other, and in from non-reduced end court
On the equidirectional for reducing end, be consequently formed microfibre.In this configuration, include the intramolecular of suitable big figure and divide
Hydrogen bond between son, thereby is achieved significant cellulose mechanical strength.
In view of the natural rich of cellulose, fiber is make use of in different industrial circles since some time
Element, and its catabolite in different phase.
As an example, according to document US5538553A, it is known that a kind of method that manufacture is used for the material of building, its bag
The aqueous suspension of containing cellulose, the aqueous suspension and sulfate solution of lime, the mixture of preferably sulfuric acid water solution.
The lime of reaction is in hydrated state, and in the presence of sulfate, it and fibrin reaction result in a kind of paste, and the paste is straight
Connect for being connected to volcanic ash and waterpower adhesive such as cement to obtain the material with good mechanical properties.
Document FR2700163A1 describes a kind of method of manufacture construction material, and it is by such reactant mixture
Obtain, suspension of the mixture comprising the cellulose fibre for coming from paper and cardboard waste in stoichiometric quantity,
Lime and unit price or trivalent metal sulfate such as aluminum sulfate.Such condition results in the lignin-sulphur of paste form
Acid-calcium aluminate, compresses it, and is then dried, or molding, is subsequently used for manufacturing machinery and acoustics and heat with attracting people's attention
The Constracture unit of insulating properties.
The applicant has been developed for a kind of method for cellulose chemistry degraded, and it includes quick lime, rather than ripe stone
Ash, this generates different from the known organic-mineral complex compound of those.Additionally, applicants have noted that this complex compound
With excellent machinery and physicochemical property, it is a kind of base material for attracting people's attention that this causes it, particularly for building field, and
Other field.
Specifically, compared with the material of above-mentioned prior art, the material of the present invention is obtained in that such Constracture unit, its
Show more preferably, this is the several performances listed hereinafter by such element supporting：
- high mechanical properties,
- high heat insulation capacity, and thermal conductivity λ is 0.1-0.7W/m DEG C (depending on component thickness), and high sound insulation energy
Power, and acoustic attenuation scope is 30-80dBa (depending on component thickness),
- high rigidity, and elastic modelling quantity is 0.9-4.3MPa (depending on component thickness).
Additionally, it is a kind of very light material, particularly than timber or Mei Sinai fiberboards, it can absorb it originally
The water of body weight, and it is indeformable, and it can be dyeed with masking liquid, and it is corrosion-resistant.
From the viewpoint of environment,, available from inexhaustible nature material, it is complete recyclable, its manufacture method for it
Not producing any toxic products, and manufacture waste can be reintroduced back in industrially preparing process.
Therefore, the present invention relates to a kind of calcium-cellulose it is organic-mineral complex compound, its can by aqueous suspension,
Quick lime reacts to prepare on cellulose.
According to the present invention, hydration of the quick lime with the reaction speed of cellulose far above quick lime in water-bearing media is fast
Degree, although two kinds of reactions (having different dynamics) coexist.
A kind of complex compound formed according to the present invention, it is by being connected to calcite CaCO3What upper polysaccharide chain was constituted, should
Polysaccharide chain is the CH entrained by the carbon 5 of the glucose unit of the fracture of the intermolecular hydrogen bonding by cellulose and cellulose2OH bases
The decarboxylation of group's (carbon 6) is forming.The latter is by the way that in reaction medium, the carbon dioxide of described decarboxylation release is coming
From the Ca (OH) being hydrated in quick lime2It is upper to react to be formed.Entrained by the fracture of intermolecular hydrogen bonding and the carbon 5 of glucose unit
CH2The decarboxylation of OH groups can be adjoint.
Favourable, in this complex compound, at least 50% non-reduced end of cellulose is according to mentioned above de-
Carboxylation carrys out decarboxylation, and preferably at least 75%, either at least 90% or or even all.Favourable, and combined with preceding feature
Or do not combine, cellulose at least 50% intermolecular hydrogen bonding disconnect, preferably at least 75%, either at least 90% or or even
All.
CH entrained by the carbon 5 of glucose unit2The decarboxylation of OH groups needs the glucose unit involved by decarboxylation
C6 hydroxyls hydrogen atom, and the fracture of the intramolecular hydrogen bond between the oxygen atom of the pyranoid ring of ensuing glucose unit.
In the complex compound forming process, other intramolecular hydrogen bonds also can rupture, and without any subsequent decarboxylation.
The structure of the complex compound of the present invention is to pass through carried out analysis to support, they some are displayed in embodiment
In 2.
The invention further relates to a kind of method for preparing calcium-cellulose complex compound, according to the method, quick lime is aqueous outstanding
React on cellulose in supernatant liquid, and complex compound is to paste form acquisition.
Pending cellulose can be provided in any form, pretreatment or unpretreated, and can be come
From in any source.It is preferred that its form in cellulose fibre, and it may come from any paper and cardboard waste, for example
Come from following cellulose waste：Recycling, waste collection center, old paper, cardboard, newspaper, magazine or other celluloses
Waste.It can also originate from paper slurry or paper waste.
The enforcement of methods described is simple, and obtains complex compound, but regardless of the composition (that is, water, quick lime and
Cellulose) addition.Their addition can be adjoint.According to a kind of favourable variant of the inventive method, by raw stone
Ash is poured in water, then introduces cellulose.It is preferred that CaO includes 30/70 to 70/30 with the mass ratio of cellulose.Favourable, it
It is 50/50, the reacting dose of quick lime is and pending cellulose identical.
Different compositions can be added in the paste obtained according to this method, and this depends on the application intended, and is selected from
The salt of the metal of aluminium, potassium, magnesium and calcium, the salt is preferably selected from calcium sulfate, phosphate, carbonate, oxalates and silicate, or
Still it is, for example, calcium stearate, aluminum oxide, cellulose powder, sawdust and/or calcium silicates.
Its outstanding performance is attributed to, in addition to building field, the complex compound of the present invention can be used for many other applications
In, such as in furniture industry, such as Furniture manufacture, ornament or panel, and civil engineering and construction applications, such as conduct
Filling plaster, gasket material and connection plaster, as being used to manufacture the material of road slab, for manufacturing roundstone and kerb.
Certainly, these applications are nonrestrictive.
Other feature and advantage of complex compound of the present invention show in following embodiment and with reference to Fig. 1-7, here：
- Fig. 1-5 illustrate control fiber element, the present invention complex compound infrared spectrum and can be in one or two kinds of sample
The superposition of these spectrum of the other chemicals found in product.
- Fig. 6 and 7 illustrates the X-ray diffraction spectra of the complex compound of control fiber element and the present invention.
Embodiment 1：The method for preparing the organic-mineral complex compound of the present invention
In this embodiment, complex compound is by coming from prepared by following cellulose waste：Recycling, waste collection
Center, old paper, cardboard, newspaper, magazine or other cellulose wastes.It can be being produced by paper slurry or paper waste.
In blender either kneader or any other 1-5m3In mixing apparatus, it is continually introduced into：
- 1000 liters of water,
- and then under gentle agitation, the calcium oxide of 180kg powder types, its purity (carrys out table higher than 95% with CaO content
Up to)；Plus the angle of incidence should be shorter than 5 minutes,
- foregoing 180kg cellulose wastes, while after the waste is added, being kept stirring for (may more strongly) 20
Minute.
During this final stage, the temperature of reaction medium is increased to 75-80 DEG C；It is actually by exothermic reaction group
Into.
Obtain the paste of the invention of 1400kg.
Embodiment 2：The sign of the organic-mineral complex compound of the present invention
Infrared spectrum analysis：
On the paste sample of the invention that embodiment 1 is obtained and in the initial fiber element sample for contrast (referred to as
Control fiber element, it is obtained by the way that initial waste is dispersed in water) on carried out infrared spectrum, it has in Buddha's warrior attendant
Decay total reflection on stone crystal.
The IR spectrum of control fiber element, and the paste for reporting embodiment 1 in fig. 2 are reported in FIG.
In figure 3, the cellulose available from the library of spectra of assay laboratory is superimposed on the spectrum (control fiber element) of Fig. 1,
Calcite (calcium carbonate) and kaolinite (aluminium hydrosilicate, formula Al2Si2O5(OH)4) spectrum.
In the diagram, the calcite and kaolinite identical spectrum with Fig. 3 is superimposed on the spectrum (present invention) of Fig. 2.
In Figure 5, it is superimposed the spectrum of Fig. 1 and 2.
With regard to control fiber element sample, features below band is observed in figures 1 and 3：
- 3345,2895,1057 and 1032cm-1Exist cellulase type sugar characteristic band；
- 1429 and 874cm-1There is the characteristic band of calcium carbonate；
- 3692,3619,1107,541 and 470cm-1There is the characteristic band of kaolinite type silicate.
With regard to the paste sample of the present invention, features below band is observed in figures 2 and 4：
- in 3413cm-1There is the characteristic band of hydroxy functional group；
- 1431 and 874cm-1There is the characteristic band of calcium carbonate；
- 3629,1112,541 and 470cm-1There is the characteristic band of silicate.
The characteristic band of cellulose is not observed, and there is the characteristic band of hydroxy functional group.In addition, in the paste of the present invention
In yet forms both different calcium carbonate.
It should also be mentioned that having been observed that the presence with the entity of wide of the mark of the present invention.They come from or constitute
For the residue of initial fiber element waste.As an example, the silicate is present in paper pulp.
Fig. 5 confirms observation mentioned above.
X-ray diffraction analysis：
The analysis on 40-300kV X-ray beam radiometer equipment, is carried out in 1.5406nm wavelength.
In figure 6, it was recently reported that the X-ray diffraction spectra of control fiber element.
In the figure 7, it was recently reported that the X-ray diffraction spectra of the calcium-cellulose complex compound of the embodiment of the present invention 1.
Compared by two spectrum, existed in the spectrum of complex compound of the present invention it was observed that between the 21 and 25 of the θ of angle 2
Obvious band, the calcite existed different from contained by control fiber element is which characterizes.
This calcite is by reaction medium, being discharged in the exothermal reaction process in quick lime on cellulose
Carbon dioxide, pyranoid ring coming from quick lime hydration Ca (OH)2On reaction being formed.
Embodiment 3：Organic-mineral the complex compound of the present invention is applied to manufacture construction material
In blender or kneader or any other mixing apparatus, introduce successively：
- water,
The aforementioned cellulose wastes of -250kg
- and then under gentle agitation, 300kg calcium oxide, it is in powder type, and purity (is contained higher than 95% with CaO
Amount expression),
- aluminum sulfate (Al2(SO4)3, 14H2O)。
The paste of the present invention is obtained after filtration.
By this paste compacting, then mould to produce Constracture unit.
Embodiment 4：The other application of the organic-mineral complex compound of the present invention
Paste shape calcium-cellulose complex compound that embodiment 1 is obtained has many applications, and they some are described below.
It can serve as external coating：The composition of a kind of paste based on the present invention and cement is prepared for, according to plan
Result determined by ratio, then the calcium stearate or zinc as water repellent is added using the ratio of 0.1-0.5% (m/m).
The composition for being obtained is it is possible thereby to apply.
It can also be used in powder form：The paste of the present invention is dried to obtain powder, by it subsequently according to plan
As a result the ratio for determining and cement mixing.
In powder type, it can prepare cement or plaster to be mixed as mixture addition, and it can have
Body is used for structural detail or panel of the manufacture with high thermal insulation and sound insulation capabilities.
Therefore, other targets of the invention are following：
A kind of-method of manufacture composite, according to the method, is prepared for the paste of aforesaid calcium-cellulose complex compound, will
Described paste shaping, and the material for being obtained is dried；
- be used for the material obtained according to methods described to manufacture sheet, breeze block, solid wood, brick, facade decoration materials；
- be used for the material obtained according to method as described above to build, construct, civil engineering, furniture and furnishing fields；
- construction or decoration element, it is manufactured by molding according to the paste for being obtained of the invention.
Claims (13)
1. a kind of calcium-cellulose it is organic-mineral complex compound, it can be by the way that in aqueous suspension, quick lime be on cellulose
React to obtain.
2. complex compound according to claim 1, it is characterised in that it is by being connected to calcite CaCO3Upper polysaccharide chain structure
Into, the polysaccharide chain is entrained by the carbon 5 of the glucose unit of the fracture of the intermolecular hydrogen bonding by cellulose and cellulose
CH2The decarboxylation of OH groups is forming.
3. complex compound according to claim 2, it is characterised in that the calcite is by the way that in reaction medium, described is de-
The carbon dioxide of carboxylation release is in the Ca (OH) for coming from quick lime hydration2It is upper to react to be formed.
4. a kind of method for preparing calcium-cellulose complex compound, it is characterised in that quick lime is added to the water, fiber is subsequently adding
Element, and obtain the complex compound of paste form.
5. method according to claim 4, it is characterised in that form of the cellulose in cellulose fibre, particularly from
Paper waste.
6. according to the method for claim 4 or 5, it is characterised in that CaO includes 30/70 to 70/30 with the mass ratio of cellulose.
7. according to the method for any one of claim 4-6, it is characterised in that by selected from least one metal of aluminium, potassium, magnesium and calcium
Salt add in the paste.
8. method according to claim 7, it is characterised in that the salt is selected from sulfate, phosphate, carbonate, oxalates and silicon
Hydrochlorate.
9. according to the method for any one of claim 4-8, it is characterised in that by calcium stearate, aluminum oxide, cellulose powder, sawdust
And/or calcium silicates is added in the paste.
10. it is a kind of manufacture composite method, it is characterised in that the paste of calcium-cellulose complex compound is according to claim 4-9
Any one shapes described paste come what is prepared, and the material for being obtained is dried.
The purposes of 11. materials obtained according to claim 10, it is used to manufacture sheet, breeze block, solid wood, brick, facade
Decoration materials.
The purposes of 12. materials obtained according to claim 10, it is used to building, constructs, civil engineering, furniture and decoration neck
Domain.
13. pastes obtained by molding claim 4, and the construction or decoration element of manufacture.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR2014/051929 WO2016012662A1 (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106660880A true CN106660880A (en) | 2017-05-10 |
Family
ID=51352717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480080895.2A Pending CN106660880A (en) | 2014-07-24 | 2014-07-24 | Calcium-cellulose organo-mineral complex, preparation process and applications |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3172179A1 (en) |
| CN (1) | CN106660880A (en) |
| WO (1) | WO2016012662A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102464540B1 (en) * | 2021-12-28 | 2022-11-09 | 김준형 | pH-responsive Cement Admixture Capable of Self-recovery of Cement Composite |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB638501A (en) * | 1946-10-25 | 1950-06-07 | John Frederick Barrow | Improvements in or relating to building material |
| GB907043A (en) * | 1960-06-03 | 1962-10-03 | Karoly Szepesi | Improvements in and relating to building blocks |
| AU540536B2 (en) * | 1979-04-17 | 1984-11-22 | Robert Gordon Leigh Bohm | Building panel material |
| FR2604102B1 (en) * | 1986-09-18 | 1988-11-10 | Air Liquide | HIGH POROSITY SILICOCALCARY MASS FOR GAS STORAGE, AND MANUFACTURING METHOD |
| US5118219A (en) * | 1991-03-21 | 1992-06-02 | Chemstar Lime Company | Method of capping tailings ponds |
| DE4110829A1 (en) * | 1991-04-04 | 1992-10-08 | Hiendl Heribert | Moulded constructional part esp. board - made from mixt. of waste paper and mineral binder |
| FR2700163B1 (en) * | 1993-01-05 | 1995-03-24 | Decros Raymond Rene Jean | Method for manufacturing a building material. |
| US5538553A (en) * | 1995-12-18 | 1996-07-23 | Burgand; Yves | Organomineral paste and method of use as construction material |
-
2014
- 2014-07-24 CN CN201480080895.2A patent/CN106660880A/en active Pending
- 2014-07-24 EP EP14750776.8A patent/EP3172179A1/en not_active Withdrawn
- 2014-07-24 WO PCT/FR2014/051929 patent/WO2016012662A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016012662A1 (en) | 2016-01-28 |
| EP3172179A1 (en) | 2017-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170510 |