CN114232380A - Papermaking deodorant and preparation and application methods thereof - Google Patents
Papermaking deodorant and preparation and application methods thereof Download PDFInfo
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- CN114232380A CN114232380A CN202111568574.5A CN202111568574A CN114232380A CN 114232380 A CN114232380 A CN 114232380A CN 202111568574 A CN202111568574 A CN 202111568574A CN 114232380 A CN114232380 A CN 114232380A
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- China
- Prior art keywords
- deodorant
- papermaking
- metal salt
- transition metal
- stirring
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- 239000002781 deodorant agent Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000003825 pressing Methods 0.000 claims abstract description 8
- -1 transition metal salt Chemical class 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 31
- 229910052723 transition metal Inorganic materials 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 23
- 238000004537 pulping Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 241000894006 Bacteria Species 0.000 abstract description 8
- 238000004332 deodorization Methods 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/12—Organo-metallic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/24—Addition to the formed paper during paper manufacture
- D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
- D21H23/28—Addition before the dryer section, e.g. at the wet end or press section
Abstract
The invention discloses a papermaking deodorant and a preparation and application method thereof. The papermaking deodorant is an acid-removing deodorant, and can chemically react with specific acid odor pollutants which are rancid after being nourished by bacteria, so that the sour odor is slowed down or eliminated; the deodorant is mainly added for use after sheet forming in a papermaking stage and before wet pressing in a pulping and papermaking process, and the deodorization effect is achieved by utilizing the esterification reaction generated at the temperature in a drying stage, and the deacidification efficiency is over 90 percent.
Description
Technical Field
The invention belongs to the technical field of pulping and papermaking, and particularly relates to a papermaking deodorant and application thereof.
Background
The pulping and papermaking process is mainly divided into a pulping stage and a papermaking forming stage, wherein the pulping stage mainly comprises the steps of raw material selection, cooking, washing, bleaching, concentration and the like; the papermaking forming stage mainly comprises: the method comprises the steps of pulp dispersing, pulping, additive mixing, paper machine front pool, paper pulp netting, paper making and forming, wet paper squeezing, drying, press polishing, paper reeling and the like.
And peculiar smell is often generated under the influence of raw materials or process products in the pulping and papermaking processes, and the most main stink is derived from sulfides, nitrogen-containing compounds, aldehydes, acids and the like, so that deodorization treatment is required. At present, the traditional deodorant deodorization modes and addition points in pulping and papermaking are mainly two types: the common method is that deodorant is added into raw materials such as waste gas discharged by the process, sludge in slurry, white water and the like in the pulping stage to sterilize and deodorize; the other method is to add essence into the paper to physically mask and deodorize. However, acid odor pollutants which cause rancidity after the bacteria are nourished do not have a special deodorant effect.
The types of deodorants in the field of pulping and papermaking are mainly classified into physical covering and masking deodorants mainly comprising essence, deodorant for eliminating gases such as hydrogen sulfide and the like by using metal reactions such as copper sulfate/ferrous ions and the like, adsorption type sterilizing deodorants mainly comprising calcium hydroxide/calcium carbonate, oxidation degradation type deodorants mainly comprising free radical reactions and natural sterilizing, adsorption/neutralization reaction type deodorants based on natural extracting solutions. Compared with physical deodorants such as adsorption and masking and plant deodorants, the deodorant has slow deodorization effect and incomplete action, and chemical deodorants can quickly and efficiently eliminate odor by utilizing reactions such as oxidation, decomposition and neutralization and are popular with manufacturers.
On the other hand, the finished paper is easily affected by environmental temperature, humidity, time and the like in the storage process, bacteria are easily bred, and organic acid is generated to cause the problems of rancidity and the like. The acid with small molecular weight is very easy to smell in paper making, and is unacceptable to manufacturers, customers and consumers.
Disclosure of Invention
The invention aims to provide a papermaking deodorant, and a preparation method and an application method thereof, aiming at solving the problems that low molecular weight, odor and specific acid odor are easily encountered in paper making in the prior papermaking technology, and the deodorant is difficult to eliminate. Under the action of transition metal ion catalyst on the carrier, the hydroxyl matter loaded on the carrier can react with specific off-flavor acid in the paper to produce the deodorizer without off-flavor or bad-flavor ester matter.
In order to solve the technical problems, the invention adopts the following technical scheme: a deodorant for papermaking uses porous material as carrier and carries transition metal salt and fatty alcohol hydroxy compound. Wherein, the fatty alcohol hydroxyl compound is alcohol or hydroxyl-containing substance without obvious odor.
The papermaking deodorant is an acid-removing deodorant, and can chemically react with specific acid odor pollutants which are rancid after being nourished by bacteria, so that the sour odor is slowed down or eliminated; the deodorant is mainly added for use after sheet forming in a papermaking stage and before wet pressing in a pulping and papermaking process, and the deodorization effect is achieved by utilizing the esterification reaction generated at the temperature in a drying stage, and the deacidification efficiency is over 90 percent.
Preferably, the transition metal salt is one or more of silver nitrate, niobium oxalate, zirconium oxalate, cadmium nitrate and palladium chloride.
Preferably, the fatty alcohol hydroxyl compound is solid alcohol of dodecanol or above or polyethylene glycol (PEG 200, PEG 400), and the dosage of the fatty alcohol hydroxyl compound is 0.1-50 parts by weight relative to the porous material, preferably 3-50 parts by weight;
preferably, the porous material is silica, titania or zinc oxide.
Preferably, the pore diameter of the porous material is 5-40 μm.
The invention also provides a preparation method of the papermaking deodorant, which comprises the following steps:
step S1, loading of transition metal salt: putting transition metal salt into a container, adding water, stirring and dissolving uniformly; then taking a proper amount of porous material carrier, adding the dissolved metal salt solution under continuous stirring, and stirring for reaction for 0.5-5 hours to obtain a uniform suspension;
step S2, sequentially carrying out suction filtration, washing and drying on the suspension obtained in the step S1, calcining at 150-350 ℃, and grinding to obtain a transition metal salt load M1;
step S3, fatty alcohol hydroxyl loading: and (2) sequentially adding water, ethanol and a surfactant into the reactor, stirring to a uniform state, quickly stirring, slowly adding the M1 solution obtained in the step S2, uniformly stirring, continuously adding the fatty alcohol hydroxyl compound, heating the system to 20-65 ℃, reacting for 0.5-15 h, filtering, washing, suction filtering, drying, cooling, and grinding into powder to obtain the deodorant M loaded with hydroxyl and the transition metal salt.
Preferably, the amount of the transition metal salt added is 0.1 to 15%, the amount of the fatty alcohol hydroxy compound added is 0.1 to 50%, and the amount of the surfactant added is 0.1 to 3% based on the weight of the porous material carrier.
Preferably, the reaction temperature in step S3 is 20-30 ℃.
The invention also provides an application method of the papermaking deodorant, which is characterized by comprising the following steps: after the paper is sheeted in the paper making and forming stage and in the drying stage before wet pressing.
Preferably, the papermaking temperature in the drying stage is 50-160 ℃, and the drying time is 15-25 min.
Has the advantages that: compared with the prior art, the invention can generate chemical reaction with acid odor pollutants which are rancid after being nourished by bacteria, slow down or eliminate acid odor, and solve the problem of odor treatment after bacteria are bred and rancid in pulping and papermaking; the deodorant is different from the deodorant which is mainly used for deodorization in a pulping stage and a paper making stage in the prior art, and the deodorant loaded with hydroxyl is mainly added after sheet forming in the paper making stage and before wet pressing in the pulping and paper making processes, so that the temperature in the subsequent drying stage is just utilized to perform chemical reaction with acid to generate ester, the effect of removing peculiar smell is achieved, and the possibility of peculiar smell in the paper making process is reduced. The deodorant has an obvious effect, and the deacidification efficiency is over 90 percent.
Drawings
FIG. 1 is a schematic view of a dosing process for the papermaking deodorant of the present invention.
Detailed Description
The invention is further elucidated with reference to the drawings and the embodiments. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
Example 1
Step S1, 5 parts of zirconium oxalate is added to a reactor containing 200 parts of deionized water at room temperature, and stirred to dissolve. Taking 80 parts of a proper amount of silicon dioxide, adding the dissolved metal compound aqueous solution under a stirring state, stirring and reacting for 1 hour until the mixture is uniform and becomes a suspension, carrying out suction filtration, washing and drying on the porous material carrier aqueous solution loaded by the transition metal salt compound, calcining at 350 ℃, and grinding to obtain a transition metal salt loaded substance A1;
step S2, adding 0.5 part of sodium dodecyl sulfate into a solution containing 180 parts of absolute ethyl alcohol in a four-port reactor containing a thermometer, a stirring paddle, a snake-shaped reflux condenser tube and a feeding port, and stirring to be in a uniform state; increasing the rotating speed, slowly adding 40 parts of A1 into the solution, and stirring until the solution is uniform; adding 20 parts of dodecanol, reacting at 20 ℃ for 5 hours, filtering, washing, performing suction filtration, drying in a forced air drying oven at 70 ℃, cooling naturally, and grinding into powder to obtain the papermaking deodorant A which is loaded by alcohols and transition metal salts and can eliminate specific acids.
Example 2
Step S1, 0.5 part of silver nitrate and 2 parts of palladium chloride are added to a reactor containing 250 parts of deionized water at normal temperature, and stirred to dissolve. Taking 50 parts of proper amount of silicon dioxide, adding the dissolved metal compound aqueous solution under the stirring state, stirring and reacting for 1 hour until the mixture is uniform and is a suspension, carrying out suction filtration, washing and drying on the porous material carrier aqueous solution loaded by the transition metal salt compound, calcining at 350 ℃, and grinding to obtain a transition metal salt loaded material B1;
step S2, adding 1 part of sodium dodecyl sulfate into a solution containing 150 parts of absolute ethyl alcohol in a four-port reactor containing a thermometer, a stirring paddle, a snake-shaped reflux condenser tube and a feeding port, and stirring to a uniform state; increasing the rotating speed, slowly adding 30 parts of B1 into the solution, and stirring until the solution is uniform; adding 10 parts of tetradecanol, reacting at 25 ℃ for 6.5h, filtering, washing, performing suction filtration, drying in an air drying oven at 70 ℃, cooling in the air, and grinding into powder to obtain the papermaking deodorant B loaded by alcohols and transition metal salts and capable of eliminating specific acids.
Example 3
Step S1, 2 parts of cadmium nitrate and 4 parts of palladium chloride are added into a reactor containing 300 parts of deionized water at normal temperature, and stirred to dissolve. Taking 100 parts of proper amount of silicon dioxide, adding the dissolved metal compound aqueous solution under the stirring state, stirring and reacting for 1.5 hours until the mixture is uniform and is suspension, carrying out suction filtration, washing and drying on the porous material carrier aqueous solution loaded by the transition metal salt compound, calcining at 350 ℃, and grinding to obtain a transition metal salt loaded substance C1;
step S2, adding 1 part of sodium dodecyl sulfate into a solution containing 200 parts of absolute ethyl alcohol in a four-port reactor containing a thermometer, a stirring paddle, a snake-shaped reflux condenser tube and a feeding port, and stirring to a uniform state; increasing the rotation speed, slowly adding 30 parts of C1 into the solution, and stirring until the solution is uniform; adding 15 parts of PEG200, reacting for 8 hours at 30 ℃, filtering, washing, performing suction filtration, drying in a forced air drying oven at 70 ℃, cooling naturally, and grinding into powder to obtain the papermaking deodorant C loaded by alcohols and transition metal salts and capable of eliminating specific acids.
Comparative example 2
Only in step S1, 2 parts of cadmium nitrate and 4 parts of palladium chloride were added to a reactor containing 300 parts of deionized water at normal temperature, and stirred to dissolve them. Taking 100 parts of proper amount of silicon dioxide, adding the dissolved metal compound aqueous solution under the stirring state, stirring and reacting for 1.5 hours until the mixture is uniform and is suspension, carrying out suction filtration, washing and drying on the porous material carrier aqueous solution loaded by the transition metal salt compound, calcining at 350 ℃, and grinding to obtain a transition metal salt loaded substance D1;
comparative example 3
Only step S2 is performed, and 1 part of sodium dodecyl sulfate is added to a solution containing 200 parts of absolute ethyl alcohol in a four-port reactor containing a thermometer, a stirring paddle, a serpentine reflux condenser tube, and a charging port, and stirred to a uniform state; increasing the rotating speed, slowly adding 30 parts of silicon dioxide into the solution, and stirring until the silicon dioxide is uniform; adding 15 parts of PEG200, reacting at 30 ℃ for 8h, filtering, washing, performing suction filtration, drying in a forced air drying oven at 70 ℃, cooling naturally, and grinding into powder to obtain the carrier E1 loaded by the alcohol.
Description of the drawings: comparative example 1 of the patent of the invention is a blank paper sample which is not added with deodorant and is only sprayed with micromolecular acid; comparative examples 2 and 3 are the transition metal salt-only or hydroxyl group-only semi-finished deodorizers, respectively, and are the formulation tables of the ingredients of the papermaking deodorizers according to the examples and comparative examples of the present invention, as shown in tables 1 and 2:
table 1 shows the preparation of transition metal salt supports M1 (parts by mass of the components of step S1) for the examples and comparative examples of the present application:
| name (R) | Zirconium oxalate | Silver nitrate | Cadmium nitrate | Palladium chloride | Deionized water | Silicon dioxide |
| Example 1 | 5 | 200 | 80 | |||
| Example 2 | 0.5 | 2 | 250 | 50 | ||
| Example 3 | 2 | 4 | 300 | 100 | ||
| Comparative example 1 | ||||||
| Comparative example 2 | 2 | 4 | 300 | 100 | ||
| Comparative example 3 |
Table 2 shows the preparation (parts by mass) of the papermaking deodorant M in the examples and comparative examples of the present application:
| name (R) | Dodecyl sulfuric acidSodium salt | Anhydrous ethanol | M1 | Dodecanol | Tetradecanol | PEG200 |
| Example 1 | 0.5 | 180 | 40 | 20 | ||
| Example 2 | 1 | 150 | 30 | 10 | ||
| Example 3 | 1 | 200 | 30 | 15 | ||
| Comparative example 1 | ||||||
| Comparative example 2 | ||||||
| Comparative example 3 | 1 | 200 | 30 | 15 |
The invention discloses a method for evaluating the performance of a papermaking deodorant, which comprises the following steps:
the paper sample preparation with the deodorization function and the deodorant use test method comprise the following steps: taking a pulp sample with known pulp concentration, adding tap water to dilute to 1%, and adding 0.1% of the pulp sampleOrganic acid (butyric acid: caproic acid mixed and added according to the proportion of 6: 4) is added according to the proportion of 80g/m2Making into sheets by using a PL6-T type sheet making machine; the papermaking deodorant is prepared into 1% diluted solution, the diluted solution is uniformly and quantitatively sprayed on a wet paper sample, the wet paper sample is quickly squeezed for 5min under the pressure of 0.6 MPa by an L8-A type standard paper sample squeezer, the paper sample is dried for 20min at the temperature of 100 ℃ by a PL7-C type flat paper sample dryer, and the paper sample is placed in a tasteless glass bottle with a plug after being cooled by an odorless dryer, and the paper sample is sealed and stored for balancing moisture for 24h to be tested.
1. And (3) particle size testing: and carrying out particle size analysis before and after loading on the carrier by using a micro-nano Winner 2000ZD type laser particle size analyzer in the Jinan province.
2. Sensory evaluation of the smell of finished paper (refer to SN/T3179-: at least 5 evaluators with healthy posture, sensitive smell and rich experience are selected to carry out an odor evaluation experiment in a quiet, well ventilated and odor-free constant temperature and humidity environment (23 ℃, 52%). The evaluator shakes the glass bottle before measuring, opens the plug to flash or inhale the smell, and then immediately closes the plug, describes and records the smell grade; after at least 2min of pause, the next sample is again smelled, and the above operation is repeated until the end. Wherein when the first sample is opened and smelled, the evaluation should be opened again after at least 2min of re-tightening (until the smell is accumulated). After evaluation, the odor grade evaluation mean value is calculated to see the odor change, wherein the odor grade is as follows:
0= no off-flavor, no perceptible;
1= odor just perceived (poorly defined);
2= moderate odor;
3= moderate strong odor;
4= strong odor.
GCMS test: adsorbing 1g of paper sample at 40 deg.C for 30min by using Shimadzu GCMS-QP2020NX gas chromatography-mass spectrometry (GCMS) by solid phase microextraction method, analyzing for 3min, and comparing the deacidification effect of the deodorant according to the acid peak area change in the paper sample. The relevant instrument parameters were as follows:
a chromatographic column: InertCap Wax, 30 m.times.0.25 mm.times.0.25 um
Column temperature procedure: 50 ℃ (5 min) _10 ℃/min _250 ℃ (10 min)
And (3) sample introduction mode: split-flow sample injection with split-flow ratio of 5:1
The control mode is as follows: linear velocity
The collection mode is as follows: SCAN
An ionization mode: EI (El)
Ion source temperature: 200 deg.C
Interface temperature: 250 deg.C
Detector voltage: tuning voltage +0.3kV
Solvent delay time: 1min
An extraction head: merck 57348-U type SPME-50/30umDVB/CAR/PDMS
Performance evaluation results:
the indexes of the deodorant product of the invention are as follows:
1. the basic index is off-white powder;
2. taking silicon dioxide as an example, the particle size of D50 before loading the carrier is about 30 microns, the particle size of the carrier after loading the metal salt and the hydroxyl substance is slightly increased, and the particle size of D50 is about 35 microns.
Adding points: after sheet formation and before wet pressing in sheet making stage
The site where the chemical reaction occurs: drying stage
The using method comprises the following steps: spraying or mixing with other chemical agents in proportion to prepare 0.2-1% aqueous solution.
Table 3 shows sensory evaluation data of odor of paper-making in a constant temperature and humidity environment ((23 ℃, 52%)) and GCMS acid content data of the paper-making deodorant of each example and comparative example of the present invention:
| example number | Odor grade | Description of the smell | GCMS acid content (chromatogram peak area) 106 |
| Example 1 | 0.0 | Has no peculiar smell | 0.9 |
| Example 2 | 0.0 | Has no peculiar smell | 0.8 |
| Example 3 | 0.0 | Has no peculiar smell | 0.5 |
| Comparative example 1 | 4.0 | Strong peculiar smell | 12.0 |
| Comparative example 2 | 3.5 | Has obvious peculiar smell | 11.8 |
| Comparative example 3 | 3.5 | Has obvious peculiar smell | 11.6 |
As shown in the results of Table 3, compared with the comparative example, in the examples 1 to 3 of the invention, after the papermaking deodorant is added, the peculiar smell of the formed paper is eliminated through sensory evaluation, the acid content is obviously slowed down in a GCMS test, and the acid removal efficiency reaches more than 90%, which shows that the influence of the acid on the formed paper can be effectively slowed down after the papermaking deodorant is added. The paper deodorant is added for use after sheet forming in a paper making and forming stage and before wet pressing, and esterification reaction is carried out at the temperature of 50-160 ℃ in a drying stage, so that acid smell-free paper after esterification can be obtained; the reaction temperature is preferably 85-120 ℃, and the drying time is preferably 20 min.
The deodorant provided by the invention can chemically react with acidic odor pollutants which are rancid after being nourished by bacteria, so that the acidic odor is slowed or eliminated, and the problem of odor treatment after the rancid is bred by the bacteria in pulping and papermaking is solved; the deodorant is different from the deodorant which is mainly used for deodorization in a pulping stage and paper making before, the deodorant is added at different points, and the deodorant loaded with hydroxyl is mainly added after sheet forming in a paper making forming stage and before wet pressing in the pulping and paper making processes, so that the deodorant reacts with acid to generate ester just by utilizing the temperature in a subsequent drying stage, and the effect of removing peculiar smell is achieved. The deodorant has an obvious effect, and the deacidification efficiency is over 90 percent.
Claims (10)
1. A papermaking deodorant is characterized in that: takes a porous material as a carrier and is loaded with transition metal salt and fatty alcohol hydroxyl compound.
2. The deodorant for papermaking according to claim 1, wherein: the transition metal salt is one or a combination of more of silver nitrate, niobium oxalate, zirconium oxalate, cadmium nitrate and palladium chloride.
3. The deodorant for papermaking according to claim 1, wherein: the fatty alcohol hydroxyl compound is solid alcohol or polyethylene glycol of dodecanol or above.
4. The deodorant for papermaking according to claim 1, wherein: the porous material is silicon dioxide, titanium dioxide or zinc oxide.
5. The deodorant for papermaking according to claim 1, wherein: the pore diameter of the porous material is 5-40 mu m.
6. A method for preparing a deodorant for papermaking according to any one of claims 1 to 5, characterized by comprising the steps of:
step S1, loading of transition metal salt: putting transition metal salt into a container, adding water, stirring and dissolving uniformly; then taking a proper amount of porous material carrier, adding the dissolved metal salt solution under continuous stirring, and stirring for reaction for 0.5-5 hours to obtain a uniform suspension;
step S2, sequentially carrying out suction filtration, washing and drying on the suspension obtained in the step S1, calcining at 150-350 ℃, and grinding to obtain a transition metal salt load M1;
step S3, fatty alcohol hydroxyl loading: and (2) sequentially adding water, ethanol and a surfactant into the reactor, stirring to a uniform state, quickly stirring, slowly adding the M1 solution obtained in the step S2, uniformly stirring, continuously adding the fatty alcohol hydroxyl compound, heating the system to 20-65 ℃, reacting for 0.5-15 h, filtering, washing, suction filtering, drying, cooling, and grinding into powder to obtain the deodorant M loaded with the alcoholic hydroxyl and the transition metal salt.
7. The method for producing a deodorant for papermaking according to claim 6, characterized in that: the addition amount of the transition metal salt is 0.1-15%, the addition amount of the fatty alcohol hydroxyl compound is 0.1-50%, and the addition amount of the surfactant is 0.1-3% of the weight of the porous material carrier.
8. The method for producing a deodorant for papermaking according to claim 6, characterized in that: in the step S3, the reaction temperature is 20-30 ℃.
9. A method for using the papermaking deodorant according to any one of claims 1 to 5, characterized in that: after the paper is formed into sheets in the papermaking forming stage and in the drying stage before wet pressing, the paper is added and used in a spraying mode.
10. The method of applying a deodorant for papermaking according to claim 9, wherein: in the drying stage, the papermaking temperature is 50-160 ℃, and the drying time is 15-25 min.
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| JPS63130136A (en) * | 1986-11-20 | 1988-06-02 | Nippon Kayaku Co Ltd | Deodorant |
| JPH08187278A (en) * | 1995-01-10 | 1996-07-23 | Nippon Shokubai Co Ltd | Deodorant and deodorization using the same |
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