EP3898550A1 - A cementitious composition with photocatalytic activity - Google Patents
A cementitious composition with photocatalytic activityInfo
- Publication number
- EP3898550A1 EP3898550A1 EP19820803.5A EP19820803A EP3898550A1 EP 3898550 A1 EP3898550 A1 EP 3898550A1 EP 19820803 A EP19820803 A EP 19820803A EP 3898550 A1 EP3898550 A1 EP 3898550A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- clinker
- carbon nitride
- cement
- cementitious composition
- photocatalytic
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 72
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004568 cement Substances 0.000 claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 claims abstract description 46
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 poly(heptazine imide Chemical class 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 239000000809 air pollutant Substances 0.000 claims abstract description 6
- 231100001243 air pollutant Toxicity 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000004570 mortar (masonry) Substances 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000004567 concrete Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000011083 cement mortar Substances 0.000 claims description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000006072 paste Substances 0.000 description 14
- 239000002243 precursor Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/128—Heterocyclic nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
- B01D2255/2027—Sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
- C04B2111/00827—Photocatalysts
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
-
- 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
- C04B2290/00—Organisational aspects of production methods, equipment or plants
- C04B2290/20—Integrated combined plants or devices, e.g. combined foundry and concrete plant
Definitions
- the present invention relates to a photocatalytic cementitious
- the photocatalytic cementitious composition for the degradation of pollutants, the decontamination of the environment, and the prolonged retention of the superficial appearance.
- the photocatalytic cementitious composition is surprisingly activated by visible light. Further, the invention relates to methods of manufacturing photocatalytic cementitious compositions and the obtained product as well as to a device for carrying out the method.
- Photocatalytic cementitious compositions which may be applied to various substrates in order to improve the preservability and to reduce the charge of environmental pollutants have long been known.
- the photocatalytic layer obtainable by the photocatalytic cement composition applied to said substrates may oxidize and/or decompose a variety of pollutants present in the environment in gaseous or microparticulate form, for instance N-oxides, polycondensed aromatic hydrocarbons, benzene, etc.;
- photocatalysis converts the above said pollutants into simpler particles, which are non volatile and may easily be washed away, thus preventing their further propagation in the atmosphere, as well as restraining the contaminant action thereof on the treated substrate.
- TiC>2 and other stable metal oxide photocatalysts suffer from no or limited visible light absorption due to their large band gap (Kasahara, A.; Mukumizu, K.; Hitoki, G.; Takata, T.; Kondo, J. N.;Hara, M.; Kobayashi, H.; Domen, K. J. Phys. Chem. B 2003, 107, 791 -797; Maeda, K.; Teramura, K.; Lu,
- this material has a band gap of about 2.7 eV and consequently it can absorb light up to 450 nm (in visible field).
- it is first discovered as visible light photocatalyst by Wang et al. in 2009 Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin,
- Graphitic carbon nitride also indicated as g-C3N4, is the most attractive as a potential photocatalyst due to its 2D structure similar to graphene, thermal and chemical stability, moderate band gap and low cost (X. Wang, K. Maeda, Ar. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K. Domen, M. Antonietti, A metal- free polymeric photocatalyst for hydrogen production from water under visible light, Nat. Mater. 8 (2009) 76-80; Z. Wang, W. Guan, Y. Sun, F. Dong, Y. Zhou, W.-K.
- the inventors of the present invention have surprisingly found a cementitious composition for the degradation of pollutants, the decontamination of the environment, and the prolonged retention of the superficial appearance, activated by visible light. It was further surprisingly found that a specific manu- facturing method provides appreciable photocatalytic activity with small effort.
- the present invention relates to a cementitious composition
- a cementitious composition comprising:
- embodiment consisting of at least an alkaline metal salt of poly(heptazine imide);
- the invention further relates to a method of manufacturing a photocatalytic cementitious composition comprising: - manufacturing cement clinker
- the invention also relates to the obtained photocatalytic cementitious composition.
- the invention relates to a device for manufacturing a photocatalytic cementitious composition
- a device for manufacturing a photocatalytic cementitious composition comprising a rotary kiln, a cooler, a bypass, a flash reactor, and a mill
- the rotary kiln is adapted to sinter a raw material into cement clinker
- the bypass is adapted to transfer a preferbaly variable part of the clinker out of the cooler into the flash reactor
- the flash reactor is designed to receive a carbon and nitrogen providing material, mix it with the transferred clinker and react it in the presence of the clinker into an activated carbon nitride
- the mill is designed to grind the mixture comprising clinker and activated carbon nitride to provide the photocatalytic cementitious composition.
- the inventors specifically found out the use of activated carbon nitride as a photocatalyst in a cement composition for preparing paste and/or mortar and/or concrete can allow to produce a photocatalytic product, being said photocatalyst active by visible light.
- Hydraulic binder is a finely ground inorganic material which, when mixed with water, forms a paste which sets and hardens by means of hydration reaction and which, after hardening retains its strength and stability even under water.
- hydraulic binder all kinds of cements can be cited, as defined and classified in the UNI EN 197-1 : 201 1 , UNI EN 413-1 :201 1 , and UNI EN 15368:2010;
- “paste” is a hydraulic binder that has been mixed with water
- “mortar” is a mixture of cement paste and sand used in thin layers, it is a specific type of concrete with a small maximum aggregate size, as defined and classified in the UNI EN 998-1 :2016, and UNI EN 1504:2005;
- cement is a mixture of sand, gravel, and rocks held together by cement paste, as defined and classified in the UNI EN 206-1 :2016;
- activated carbon nitride denotes graphitic carbon nitride, g-C3N4, that has been doped e.g. with alkali metal ions, either by reaction with alkali or by manufacturing the carbon nitride in the presence of cement clinker or cogrinding the carbon nitride with cement clinker;
- alkaline metal salt of poly(heptazine imide) means a special activated carbon nitride, namely a salt of an alkaline metal of poly(heptazine imide), preferably the sodium salt.
- the present invention relates to new photocatalytic cement compositions capable to be added to water in order to have a paste, a mortar or a concrete for the degradation of pollutants, the decontamination of the environment, and the prolonged retention of the superficial appearance, activated by visible light.
- the invention relates to a use of a alkaline metal salt of poly(heptazine imide) for preparing a whole or a part of photocatalytic product, preferably a photocatalytic paste, a photocatalytic mortar or a photocatalytic concrete.
- the invention relates to a method for manu facturing the photocatalytic cementitious composition by either making the activated carbon nitrode by reacting suitable precurors in the presence of cement clinker in a flash reactor or by cogrinding carbon nitride made in a flash reactor with cement clinker.
- the invention relates to photocatalytic
- the photocatalyst of the invention is then part of the cementitious composition and hence being incorporated in the final mortar, paste or concrete, or in part of them.
- the photocatalyst can be part of a cementitious layer to be applied on a substrate.
- the photocatalytic cementitious composition according to the invention does not comprise T1O2, both in anatase and rutile forms.
- NOx nitrogen oxide
- the present invention relates to a cementitious composition
- a cementitious composition comprising:
- a photocatalyst comprising an activated carbon nitride, especially consisting of at least an alkaline metal salt of poly(heptazine imide);
- the cementitious composition according to the invention comprises a hydraulic binder as above defined, i.e. a finely ground inorganic material which, when mixed with water, forms a paste which sets and hardens by means of hydration reaction and which, after hardening retains its strength and stability even under water.
- a hydraulic binder as above defined, i.e. a finely ground inorganic material which, when mixed with water, forms a paste which sets and hardens by means of hydration reaction and which, after hardening retains its strength and stability even under water.
- the cementitious composition according to the present invention comprises an activated carbon nitiride as photocatalyst.
- an activated carbon nitiride as photocatalyst.
- it comprises a photocatalyst consisting of at least an alkaline salt of poly(heptazine imide).
- the present cementitious composition has photocatalytic activity and efficient photocatalytic capacity.
- photocatalytic activity refers to the capacity to obtain the abatement of contaminants under solar-simulating radiation and/or visible light radiation. The activity is conventionally measured as % NOx conversion according to standards known in the art e.g., according to UNI 11247:2010.
- the term "efficient photocatalytic capacity” refers to the capacity to obtain, comparatively, a higher abatement of contaminants under solar-simulating radiation (conventionally measured as % NO conversion, according to UNI 1 1247:2010) with respect to a commercial visible light activated T1O2.
- the at least alkaline metal salt of poly(heptazine imide) is sodium or potassium or lithium or cesium salt of poly(heptazine imide); more preferably the at least alkaline metal salt of poly(heptazine imide) is sodium salt of poly(heptazine imide) also abbreviated as "PHI-Na”.
- a further preferred activated carbon nitride is obtained by making carbon nitride with flash calcination from carbon and nitrogen providing materials either in the presence of cement clinker or with subsequent cogrinding with cement clinker.
- PHI-Na is a yellow powder, with BET surface area of about 35 m 2 /g (calculated by the Brunauer-Emmett-Teller model to adsorption isotherms, N2 at 77.4 K, for 0.05 ⁇ p/po ⁇ 0.3), a density more than 1 g/cm 3 (calculated by gas pycnometer) and having the following chemical composition
- the alternative activated carbon nitride used as photocatalyst in the cementitious composition of the invention is obtainable by flash calcination of suitable precursors.
- Carbon and nitrogen providing material such as but not limited to melamine, cyanamide, dicyanamide, guanidine hydrochloride, urea, thiourea and mixtures of two or more thereof are suitable precursors.
- melamine Especially preferred is melamine.
- Flash calcination means heating rates of at least 20 °C/minute, preferably of at least 30°C/minute. It can take place in air or nitrogen atmosphere, preferably in air. With melamine as precursor the yield of carbon nitride usually is 50 % or more.
- the flash calcination is carried out in the presence of clinker.
- a temperature in the range from 350 to 800 °C, preferably from 600 to 700 °C, most preferred of about 650 °C, is useful. Then, the reaction takes from 1 to 45 minutes, often 5 to 30 minutes and typically 15 minutes are sufficient. It is specifically beneficial to split off some clinker directly from the rotary kiln and admix the precursor. Thereby, no or only minimal heating is needed and the clinker serves to directly provide activated carbon nitride.
- the amount of carbon and nitrogen providing materials depends on the amount of photocatalyst desired and the necessary photocatalytic activity of the cementitious composition. Usually,
- the carbon nitride is made by flash calcination of suitable precursors without additions.
- the obtained carbon nitride is mixed with clinker and coground to provide the photocatalytic cementitious composition comprising the activated carbon nitride. Typically, the clinker is cooled before grinding. The carbon nitride can be cooled, too, or be mixed with the clinker as it comes out of the flash calcination.
- the device for carrying out the method according to the invention comprises a usual cement manufacturing plant and adds a flash reactor to make the activated carbon nitride.
- a flash reactor to make the activated carbon nitride.
- the novel feature besides the reactor is a bypass adapted to take off a - preferably variable - part of the clinker from the cooler. That means, hot clinker is split off out of the cooler.
- Means for transfer into the flash reactor pass it to the carbon nitride manufacturing.
- the flash reactor additionally receives carbon and nitrogen providing materials, preferably melamine. It is advantageous when the carbon and nitrogen providing materials have a small particle size, e.g. from 10 to 150 pm, to enable good distribution and fast heating on the clinker nodules. If needed, the reactor can be equippped with a heating system.
- the cementitious composition according to the invention does not comprise T1O2, both in anatase and rutile forms.
- the present invention relates to new photocatalytic
- cementitious compositions capable to be added to water in order to have a cement product, preferably a cement paste, a cement mortar or a cement concrete for the degradation of pollutants, the decontamination of the environment, and the prolonged retention of the superficial appearance, activated by visible light.
- the invention relates to a use of activated carbon nitride, especially an alkaline metal salt of poly(heptazine imide), for preparing a whole or a part of cement product, preferably a photocatalytic paste, a
- the photocatalyst of the invention is then part of the cementitious composition and hence being incorporated in the final cementitious product selected from a mortar, a paste and a concrete, or in part of them.
- the photocatalyst can be part of a cementitious layer to be applied on a substrate, preferably a cementitious product.
- the photocatalyst is incorporated in and/or on at least a portion of the cementitious products which could be selected from the group consisting of cementitious pastes, mortars and concretes.
- One preferred photocatalyst is poly(heptazine imide) sodium salt, called PHI-Na which is advantageously randomly distributed in the cement product and/or on the surface of the cement product.
- Another preferred photocatalyst is activated carbon nitride obtained from suitable precursors by flash calcination, either in the presence of clinker or with subsequent cogrinding with clinker.
- the cementitious composition can optionally contain an aggregate.
- the "aggregate”, also known as “inerts” or “inert aggregate”, is classified in the UNI EN 206 standard.
- the aggregate can be a fine aggregate such as sand, or a coarse aggregate such as gravel.
- the cement products made of the cementitious composition of the invention are obtained by addition of water to the cementitious composition of the invention. Typically, but not exclusively, the amount of water to be added is ex pressed with respect to the hydraulic binder contained in the cementitious com position.
- the water/binder ratio (w/w) is preferably in the range from 0.3 to 0.7.
- Cement products obtained through adding water to the aforesaid cementitious compositions, may include, without limitation, both cement pastes obtainable by cementitious compositions of the invention without aggragates, and, in some embodiments, cementitious conglomerate products obtainable by cementitious compositios comprising at least one aggregate.
- Non-limiting conglomerate cementitious products include mortars obtainable by adding water to the cementitious composition of the invention comprising also fine aggregates, and concretes obtainable by adding water to the cementitious composition of the invention comprising also fine aggregate and coarse aggregate.
- the amount of aggregate, the water/hydraulic binder ratio (w/w) and the mixing method used to form cementitious products are those used conventionally in this sector.
- the surface of the final cement products can be roughened so as to increase the specific surface in contact with the air.
- the amount of photocatalyst is preferably in an amount below or equal to 10 % with respect to the amount of the hydraulic binder, preferably from 0.01 % to 10 % by weight with respect to the amount of the hydraulic binder. In some embodiments, the range is from 1 % to 5%, preferably from 2% to 4% by weight with respect to the amount by weight of the hydraulic binder.
- the photocatalytic activity of the cementitious composition comprising PHI-Na photocatalyst was evaluated by NOx abatement procedure. [0054] The following procedure was used in order to have a method aimed at assessing the index of photocatalytic abatement due to the action of photocatalytic materials.
- NOx 0.55 ppm of NOx
- the surface of the samples S was 61 cm 2 .
- the sample to be investigated was collocated inside the reaction chamber containing a blue led visible lamp such that, at the specimen level, having a wavelength peak between 400 and 500 nm.
- the irradiation system provided an average illuminance of 4000 lux on the specimen surface during the test.
- Example 1 Evaluation of the photocatalytic activity of catalysts
- PHI-Na Sodium salt of poly(heptazine imide)
- AHP200 T1O2 provided by Sachtleben g-C3N4: graphitic carbon nitride (provided by Fairland technology) vip7000: T1O2, i.e. doped titanium dioxide Kronos vlp 7000 - a visible light activated photocatalyst)
- Table 1 index of photocatalytic abatement A c due to the action of photocatalytic materials
- Example 2 Evaluation of the photocatalytic activity of a mortar obtainable by the composition of the invention
- the photocatalytic index determination of the mortars was performed on the basis of the UNI 11247:2010, adopting two percentages of the photocatalysts, 2 % and 4 %, by weight of hydraulic binder.
- the photocatalysts were used in substitution of the same quantity of cement.
- Mortar sample preparation was done by mixing the raw materials in predetermined amounts, following the indications of the UNI EN 196-1 :2016:
- PHI-Na Sodium salt of poly(heptazine imide)
- g-C3N4 graphitic carbon Nitride (provided by Fairland technology)
- vip7000 T1O2, i.e. doped titanium dioxide Kronos vlp 7000 - a visible light activated photocatalyst).
- the cementitious compositions of the invention comprising PHI-Na in the respective amounts of 2 % and 4 % was surprisingly more active when subjected to visible light than to UV light.
- PHI-Na was more photocatalytically active at visible light than at UV light.
- the remaining catalysts of the prior art resulted to be insufficiently photocatalytically active at visible light, even if they were more active at UV light field than the PHI-Na.
- Example 3 Method for manufacturing photocatalvtic cementitious composition
- FIG. 2 shows a scheme of a device according to the invention.
- the device comprises a rotary kiln 1 , a cooler 2, a bypass 3, and a flash reactor 4.
- a raw material is sintered into cement clinker C.
- the clinker C is passed into the cooler 2, usually a grate cooler.
- the bypass 3 transfers a part of the clinker C into the flash reactor 4, which can be e.g. an insulated screw mixing system.
- the flash reactor 4 also receives a carbon and nitrogen providing material as precursor P for carbon nitride.
- a gas G either air or an inert gas like nitrogen, is insufflated in countercurrent.
- the composition is cooled in a second cooler 5 and ground in a mill not shown in the figure.
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EP18214192.9A EP3670469A1 (en) | 2018-12-19 | 2018-12-19 | A cementitious composition with photocatalytic activity under visible light |
PCT/EP2019/086060 WO2020127559A1 (en) | 2018-12-19 | 2019-12-18 | A cementitious composition with photocatalytic activity |
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EP19820803.5A Withdrawn EP3898550A1 (en) | 2018-12-19 | 2019-12-18 | A cementitious composition with photocatalytic activity |
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CN113210005B (en) * | 2021-06-02 | 2022-07-26 | 成都理工大学 | Cl-doped C 3 N 5 And method for preparing the same |
CN113956072B (en) * | 2021-11-22 | 2022-11-22 | 山东汉博昱洲新材料有限公司 | Cement carbonized body and preparation method thereof |
CN115259768A (en) * | 2022-08-31 | 2022-11-01 | 重庆交通大学 | Modified graphite phase carbon nitride type photocatalytic cement mortar and preparation method thereof |
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IT1286492B1 (en) | 1996-08-07 | 1998-07-15 | Italcementi Spa | HYDRAULIC BINDER WITH IMPROVED COLOR CONSTANCE PROPERTIES |
ITMI20030291A1 (en) | 2003-02-18 | 2004-08-19 | Italcementi Spa | SOLID FOR CEMENTITIOUS PHOTOCATALYTIC FLOORING |
AT507756B1 (en) * | 2008-12-17 | 2010-12-15 | Holcim Technology Ltd | METHOD FOR PRODUCING PHOTOCATALYTICALLY ACTIVE KLINKER |
JP5582545B2 (en) * | 2009-10-20 | 2014-09-03 | 独立行政法人産業技術総合研究所 | Photocatalyst containing carbon nitride, method for producing the same, and air purification method using the photocatalyst |
DE102012007529B4 (en) * | 2012-04-17 | 2016-03-31 | Technische Universität Bergakademie Freiberg | Imido-s-heptazine derivatives - Process for their preparation and their uses |
CN107986693B (en) * | 2017-12-11 | 2020-11-24 | 南京倍立达新材料系统工程股份有限公司 | Photocatalytic light-transmitting cement product and production method thereof |
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