WO2021059334A1 - Method for treating palm coconut seed husks - Google Patents
Method for treating palm coconut seed husks Download PDFInfo
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- WO2021059334A1 WO2021059334A1 PCT/JP2019/037317 JP2019037317W WO2021059334A1 WO 2021059334 A1 WO2021059334 A1 WO 2021059334A1 JP 2019037317 W JP2019037317 W JP 2019037317W WO 2021059334 A1 WO2021059334 A1 WO 2021059334A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- calcium silicate
- porous calcium
- palm coconut
- silicate hydrate
- coconut seed
- Prior art date
Links
- 235000013162 Cocos nucifera Nutrition 0.000 title claims abstract description 68
- 244000060011 Cocos nucifera Species 0.000 title claims abstract description 68
- 239000010903 husk Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 86
- 239000000378 calcium silicate Substances 0.000 claims abstract description 80
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 80
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000008187 granular material Substances 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 2
- 235000019645 odor Nutrition 0.000 description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 21
- 150000001735 carboxylic acids Chemical class 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LPLLVINFLBSFRP-UHFFFAOYSA-N 2-methylamino-1-phenylpropan-1-one Chemical compound CNC(C)C(=O)C1=CC=CC=C1 LPLLVINFLBSFRP-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000132539 Cosmos Species 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Definitions
- the present invention relates to a method for treating palm coconut seed husks for effectively suppressing the generation of unpleasant odors from palm coconut seed husks.
- PKS Palm Kernel Shell
- Palm coconut seed husks are desirable as fuel because they generate more than 10 million tons per year as a by-product of the palm oil industry, have a high calorific value of 4000 kcal / kg or more, and have a small amount of ash when fired. It has characteristics. On the other hand, since palm coconut seed husks contain a large amount of fatty acids including lower fatty acids such as caprylic acid and capric acid, it is necessary to take measures against unpleasant odors when handling a large amount.
- Patent Document 1 discloses a method for storing palm coconut seed husks, which comprises heat-treating at a temperature of 80 ° C. or higher using extracted steam generated from a power generation facility and then storing the seed husks. ..
- Patent Document 2 discloses the total water content of palm coconut seed husks, which includes a heat treatment step at 115 ° C. or higher, is adjusted to 7 to 15% by mass, and the oil content is further reduced to 10 mg or less per 1 g of palm coconut seed husks.
- the handling method to adjust is disclosed.
- Patent Document 1 or Patent Document 2 requires a heat source at a storage place, a treatment place, or the like for deodorizing the palm coconut seed husk. Therefore, there are problems that the scale of the apparatus is expanded and the processing place is restricted.
- the subject of the present invention is a method for treating palm coconut seed husks, which can effectively suppress the generation of unpleasant odor from palm coconut seed husks, even though it is a method that does not require a heat source or the like at the place of implementation.
- the purpose is to provide.
- the method for treating palm coconut seed husks according to the present invention is characterized by having a step (a) of mixing porous calcium silicate hydrate powder and granules with palm coconut seed husks generated by oil extraction. To do.
- the porous calcium silicate hydrate powder or granular material slowly dissolves in water existing in a storage environment such as adhering water, and changes the water to be weakly alkaline (pH 8 to pH 10).
- the generation of a weak alkaline environment by the porous calcium silicate hydrate powder granules suppresses the generation of an unpleasant odor from palm coconut seed husks.
- the sour odor from carboxylic acids which is the main unpleasant odor of palm coconut seed husks
- ammonia nitrogen also referred to as "ammoniae nitrogen"
- ammoniae nitrogen is formed in the palm coconut seed husks. .
- This ammonia nitrogen comes into contact with an alkaline solution, it volatilizes as ammonia and generates a peculiar pungent odor.
- This volatilization of ammonia nitrogen occurs in a large amount in a short time as the alkalinity of the solution increases. Therefore, in a weak alkaline environment (pH 8 to 10) formed by porous calcium silicate hydrate powder or granular material, Such volatilization of ammonia can also be effectively suppressed.
- the porous calcium silicate hydrate powder or granular material is a porous body having tovamorite (Ca 5 (Si 6 O 18 H 2 ), nH 2 O) as a main constituent phase, and is 50 m 2 / g to 80 m 2 It may have a specific surface area of / g.
- porous calcium silicate hydrate powder or granular material having a high specific surface area as described above the ability to adsorb odorous components is realized.
- 500 ⁇ L or more can be adsorbed per 1 g of porous calcium silicate hydrate powder or granular material. Therefore, by mixing the porous calcium silicate hydrate powder or granular material with the palm coconut seed shell, in addition to the chemical neutralization reaction, the porous calcium silicate hydrate powder or granular material itself has.
- the adsorptive capacity further enhances the effect of reducing unpleasant odors.
- the porous calcium silicate hydrate powder or granular material may have a porosity of 60% by volume to 80% by volume and a bulk specific gravity of 0.8 g / mL or less.
- the porosity of the porous calcium silicate hydrate powder or granular material is less than 60% by volume, the effect of taking in the water existing in the storage environment into the porous calcium silicate hydrate powder or granular material cannot be sufficiently obtained. In addition to the possibility, the ability to adsorb the above-mentioned unpleasant odor components is reduced. On the other hand, if there are many voids so that the porosity exceeds 80% by volume, there may be a problem that the porous calcium silicate hydrate powder granules are broken into fine particles when mixed with palm coconut seed husks. There is sex.
- the amount is 0.8 g / mL or less because the effect of incorporating the unpleasant odor component may not be sufficiently obtained and the problem of lowering the adsorption ability of the above-mentioned unpleasant odor component may occur.
- Palm coconut seed husks obtained by exploiting nuclear oil usually have a high water content of about 30% by mass. Such palm coconut seed husks are generally loaded onto a ship or the like from an open-loaded yard and transported, and the water content at that time is 17 on the surface thereof even if it is dried in the sun. It is about mass%, and exceeds 20 mass% inside. Then, the palm coconut seed husk having such a water content may cause an odor problem due to an unpleasant odor at the time of landing or storage.
- Odor components generated from palm coconut seed husks include aldehydes, carboxylic acids, esters, ketones, thiols, etc. Among them, aldehydes and carboxylic acids are the main odor components related to unpleasant odors. ..
- the method according to the present invention is characterized by having a step (a) of mixing porous calcium silicate hydrate powder or granular material with palm coconut seed husks which may generate an unpleasant odor.
- step (a) the effect of reducing the unpleasant odor is achieved. This point will be described later with reference to Examples.
- the porous calcium silicate hydrate powder or granular material used in the step (a) uses, for example, a silicon source (SiO 2 ) such as silica stone, a calcium source (CaO) such as lime, and water as main raw materials at a high temperature.
- a silicon source (SiO 2 ) such as silica stone
- CaO calcium source
- a cement-hardened material having a low aggregate content such as a product produced by a hydrothermal reaction in a pressure vessel under high pressure or a cement paste-hardened material, can be used.
- it is a porous lightweight powder or granular material having a porosity (also referred to as “porosity”) of 60% by volume to 80% by volume and a bulk specific gravity of 0.8 g / mL or less.
- the porosity of the porous calcium silicate hydrate powder or granular material in the present invention is a value measured by a mercury press-fitting porosimeter, and the bulk specific gravity of the porous calcium silicate hydrate powder or granular material is JIS A 5430. It is a measured value by the method according to the procedure concerning the calcium silicate board of "fiber reinforced cement board".
- the size of the porous calcium silicate hydrate powder or granular material used in the step (a) is arbitrary by, for example, crushing and classifying the cured porous calcium silicate hydrate obtained by a hydrothermal reaction. It is possible to adjust the size of. However, from the viewpoint of facilitating recovery for reusing the porous calcium silicate hydrate powder and granules after use, which will be described later, stratification is possible for palm coconut seed husks having a size of several cm. It is preferably a porous calcium silicate hydrate powder or granular material having a large size of 5 mm or less. That is, the porous calcium silicate hydrate powder or granular material used in the step (a) preferably has a particle size of 5 mm or less.
- the particle size of the porous calcium silicate hydrate powder or granular material in the present invention is the smallest mesh size among the mesh sieves (sieves) through which the porous calcium silicate hydrate powder or granular material can pass. Refers to.
- the porous calcium silicate hydrate powder or granular material used in the step (a) may be produced for deodorizing palm coconut seed husks, as long as it has the above characteristics.
- a product manufactured for other purposes such as a water quality / bottom sediment purification material or a lightweight cellular concrete may be diverted.
- the treatment method of the present invention also leads to providing an effective utilization method of scraps and the like generated in the production of lightweight aerated concrete.
- step (a) by mixing the porous calcium silicate hydrate powder and granules with the palm coconut seed shell, the porous calcium silicate hydrate powder and granules are slowly dissolved in water. Then, the water is changed to weakly alkaline (pH 8 to 10). As a result, a chemical neutralization reaction with the above-mentioned aldehydes, carboxylic acids and the like as an odor component generated from palm coconut seed husks occurs, and an unpleasant odor is reduced.
- Pore water derived from the atmosphere is always present in the pores of the porous calcium silicate hydrate powder and granules placed in the atmosphere, and adsorbed water derived from the atmosphere is also present on the surface other than the pores. Since it is present and calcium silicate hydrate is always dissolved in those waters, the surface of the porous calcium silicate hydrate powder and granules retains weak alkalinity at around pH 10. Therefore, the porous calcium silicate hydrate powder or granular material used in the step (a) does not require any special pretreatment for implementation. However, in order to more effectively cause the above-mentioned chemical neutralization reaction, the porous calcium silicate hydrate powder or granular material is previously wetted with water to increase the water content in the step (a). It does not matter if it is used in.
- the ammonia volatilized from the palm coconut seed shell in a highly alkaline environment dissolves in the water. Therefore, the effect of reducing ammonia perceived as an unpleasant odor can also be obtained.
- the method for increasing the water content of the porous calcium silicate hydrate powder or granular material is not particularly limited, and a usual method such as sprinkling water or immersing in water may be used.
- the excessive water content makes it difficult to quickly increase the alkalinity of the water and may promote the decay of palm coconut seed husks. Therefore, the water content should be 60% by mass or less. Is preferable, and more preferably 30% by mass or more and 50% by mass or less.
- the method for measuring the water content of the porous calcium silicate hydrate powder or granular material is, for example, the test described in JIS A1125 “Aggregate water content test method and surface water content test method based on water content”. It can be obtained from the method, that is, the mass of the porous calcium silicate hydrate powder or granular material before and after becoming constant at a drying temperature of 105 ⁇ 5 ° C.
- the method of mixing the palm coconut seed husk and the porous calcium silicate hydrate powder or granular material is not particularly limited as long as both can be mixed well.
- a common method for mixing powders and granules can be used, such as mixing using a powder or granular material mixing device, mixing with a heavy machine, or mixing with a transport device such as a belt conveyor.
- the timing (timing) of performing the mixing treatment according to the step (a) on the palm coconut seed husks is limited from the time when the palm coconut seed husks are produced to the time when they are stored and transported. It's not something. However, from the viewpoint that it is preferable to carry out the process when the generation of unpleasant odor is low, the mixing treatment according to the step (a) is carried out on the palm coconut seed husks immediately after being squeezed and produced. Is preferable. That is, it is most preferable that the mixing treatment according to the step (a) is performed at the palm coconut seed husk supply area.
- the amount (mixing amount) of the porous calcium silicate hydrate powder granules used in the mixing treatment according to the step (a) is the palm coconut seed husk and the porous calcium silicate hydrate powder obtained after the mixing treatment. It is preferably 2 parts by mass to 50 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and particularly preferably 5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the mixture of granules. ..
- the amount of the porous calcium silicate hydrate powder or granular material used in the step (a) is less than 2 parts by mass with respect to 100 parts by mass of the mixture, the effect of reducing the unpleasant odor is sufficiently obtained. It may not be possible.
- the amount of the porous calcium silicate hydrate powder or granular material used in the step (a) exceeds 50 parts by mass with respect to 100 parts by mass of the mixture, the ratio of palm coconut seed husks to the mixture. May cause the problem of low levels.
- the amount of water may include the amount of water due to the above water content treatment.
- Palm coconut seed husks mixed with porous calcium silicate hydrate powder and granules can be used as fuel as they are, but by containing porous calcium silicate hydrate powder and granules, they can be used as fuel. It is expected that the characteristics of will change. Further, the porous calcium silicate hydrate powder or granular material remaining after mixing still has a deodorizing effect and can be reused. From these points of view, after performing step (a), in the pre-stage of use as fuel, from a mixture of palm coconut seed husk and porous calcium silicate hydrate powder granules, porous calcium silicate hydrate powder It is preferable to separate and recover the granules.
- porous calcium silicate hydrate powder or granular material When recovering the porous calcium silicate hydrate powder or granular material from the mixture, for example, a sieve having a mesh size of 6 mm to 9 mm is used, and the porous calcium silicate hydrate powder or granular material that has passed through this sieve is recovered. be able to.
- fibers derived from palm coconut seed husks mixed in the sieve-passed portion can be separated and recovered by wind-sorting the sieve-passed portion.
- the recovered porous calcium silicate hydrate powder or granular material may be used again for the mixing treatment according to the step (a).
- the porous calcium silicate hydrate powder granules have the ability to fix sulfur oxides as a desulfurizing agent when burned together with palm coconut seed husks in a boiler or the like. Therefore, after the step (a) is completed, some of the porous calcium silicate hydrate powders and granules are intentionally removed without removing all of the remaining porous calcium silicate hydrate powders and granules. You may use it as fuel while leaving it.
- the odor was evaluated and the water content of the porous calcium silicate hydrate powder was evaluated as follows.
- the odor components generated in the head space of the wide-mouthed bottle were measured by an odor sensor (XP? 329IIIR manufactured by New Cosmos Electric Co., Ltd.) as a comprehensive quantitative measurement of the odor, and two components of carboxylic acid and ammonia as specific odors.
- a detector tube (carboxylic acid: 81L manufactured by Gastec Co., Ltd., ammonia: 105SE manufactured by Komei Rikagaku Kogyo Co., Ltd.).
- the above measurement was performed on each day 1 day, 4 days, 7 days, and 10 days after the sample was sealed in the wide-mouthed bottle.
- -Palm palm seed husks Tenera seed husks (made in Malaysia). Those 2 weeks or more after the oil squeezing treatment were collected in Japan. It had an elliptical shape with a major axis of about 25 mm and a minor axis of about 10 mm.
- -Porous calcium silicate hydrate powder granules "Ceraclean" (registered trademark) manufactured by Taiheiyo Cement Co., Ltd.
- the white granules had a particle size of 1 mm to 4 mm, a bulk specific gravity of 0.41 g / mL, a specific surface area of 77 m 2 / g, and a porosity of 67% by volume.
- -Slaked lime powder. The pH of the surface of the powder or granular material obtained by mixing with twice the amount of water was 12.5.
- Table 1 below shows each level to be measured.
- palm coconut seed husks which are the source of odor
- constant (800 g) at each level when mixing porous calcium silicate hydrate powder and granules and hydrous slaked lime, the outside is used. It was split and mixed.
- Level 1 is the case where the porous calcium silicate hydrate powder and granules are not mixed with the palm coconut seed husk, which corresponds to a comparative example.
- Level 2 is a case where slaked lime powder granules obtained by kneading with twice the amount of water are mixed with palm coconut seed husks, which corresponds to a comparative example.
- Levels 3 to 5 correspond to the case where porous calcium silicate hydrate powders and granules having a water content of 0% by mass are mixed with palm coconut seed husks in different mixing amounts.
- Levels 5 to 7 correspond to the case where porous calcium silicate hydrate powders and granules having different water contents are mixed with palm coconut seed husks in a state where the mixing amount is constant. These levels 3-7 correspond to the examples. At levels 5 to 7, the water content of the porous calcium silicate hydrate powder granules was adjusted by spraying a predetermined amount of water before mixing.
- Table 2 shows the results of odor evaluation for each level 1 to 7 shown in Table 1.
- the description "> 10” means that the numerical value was larger than 10
- the description " ⁇ 0.5” means that the numerical value was less than 0.5.
- the description "-” means that it has not been measured.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Fats And Perfumes (AREA)
- Edible Oils And Fats (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Provided is a method that does not require a heat source or the like at the place of implementation, but effectively suppresses the generation of an unpleasant odor from palm coconut seed husks. A method for treating palm coconut seed husks according to the present invention includes a step (a) for mixing porous calcium silicate hydrate powder with palm coconut seed husks generated by oil extraction.
Description
本発明は、パーム椰子種子殻からの不快臭の発生を効果的に抑制するためのパーム椰子種子殻の処理方法に関する。
The present invention relates to a method for treating palm coconut seed husks for effectively suppressing the generation of unpleasant odors from palm coconut seed husks.
再生可能エネルギー特別措置法の施行などにより、発電用ボイラ等での代替燃料として、パーム椰子種子殻（ＰＫＳ：Palm Kernel Shell、以後「パーム椰子種子殻」と呼ぶ場合もある。）を使用する技術開発が進められている。
Technology that uses palm coconut seed husks (PKS: Palm Kernel Shell, hereinafter sometimes referred to as "palm coconut husks") as an alternative fuel for power generation boilers, etc. due to the enforcement of the Act on Special Measures Concerning Renewable Energy. Development is in progress.
パーム椰子種子殻は、パーム油産業の副産物として年間１千万ｔ以上発生することに加え、４０００ｋｃａｌ／ｋｇ以上の高い発熱量を有し、且つ焼成した際の灰分量が少ない等、燃料として望ましい特徴を有する。一方で、パーム椰子種子殻は、カプリル酸やカプリン酸等の低級脂肪酸をはじめとした多種多量の脂肪酸が含まれているため、大量に扱う場合には不快臭への対策が必要となる。
Palm coconut seed husks are desirable as fuel because they generate more than 10 million tons per year as a by-product of the palm oil industry, have a high calorific value of 4000 kcal / kg or more, and have a small amount of ash when fired. It has characteristics. On the other hand, since palm coconut seed husks contain a large amount of fatty acids including lower fatty acids such as caprylic acid and capric acid, it is necessary to take measures against unpleasant odors when handling a large amount.
例えば、下記特許文献１には、発電設備から発生する抽気蒸気を使用して８０℃以上の温度で加熱処理した後、貯蔵することを特徴とするパーム椰子種子殻の貯蔵方法が開示されている。また、下記特許文献２には、１１５℃以上での熱処理工程を含む、パーム椰子種子殻の全含水率を７～１５質量％に調整し、更に含油率をパーム椰子種子殻１ｇあたり１０ｍｇ以下に調整する取扱方法が開示されている。
For example, Patent Document 1 below discloses a method for storing palm coconut seed husks, which comprises heat-treating at a temperature of 80 ° C. or higher using extracted steam generated from a power generation facility and then storing the seed husks. .. Further, in Patent Document 2 below, the total water content of palm coconut seed husks, which includes a heat treatment step at 115 ° C. or higher, is adjusted to 7 to 15% by mass, and the oil content is further reduced to 10 mg or less per 1 g of palm coconut seed husks. The handling method to adjust is disclosed.
しかしながら、特許文献１又は特許文献２に開示されている方法は、パーム椰子種子殻の消臭処理のために貯蔵場所や処理場所等での熱源を必須とする。このため、装置規模が拡大したり、処理場所に制約を有するといった課題がある。
However, the method disclosed in Patent Document 1 or Patent Document 2 requires a heat source at a storage place, a treatment place, or the like for deodorizing the palm coconut seed husk. Therefore, there are problems that the scale of the apparatus is expanded and the processing place is restricted.
従って、本発明の課題は、実施場所において熱源等を必要としない方法でありながらも、パーム椰子種子殻からの不快臭の発生を効果的に抑制することができる、パーム椰子種子殻の処理方法を提供することを目的とする。
Therefore, the subject of the present invention is a method for treating palm coconut seed husks, which can effectively suppress the generation of unpleasant odor from palm coconut seed husks, even though it is a method that does not require a heat source or the like at the place of implementation. The purpose is to provide.
本発明者らは、鋭意検討の結果、パーム椰子種子殻に特定の無機粉粒体を混合することによって、パーム椰子種子殻から発生する不快臭が効果的に低減できることを見出し、本発明を完成するに至った。
As a result of diligent studies, the present inventors have found that by mixing a specific inorganic powder or granular material with a palm coconut seed husk, the unpleasant odor generated from the palm coconut seed husk can be effectively reduced, and the present invention has been completed. I came to do it.
すなわち、本発明に係るパーム椰子種子殻の処理方法は、搾油されて発生したパーム椰子種子殻に、多孔質ケイ酸カルシウム水和物粉粒体を混合する工程（ａ）を有することを特徴とする。
That is, the method for treating palm coconut seed husks according to the present invention is characterized by having a step (a) of mixing porous calcium silicate hydrate powder and granules with palm coconut seed husks generated by oil extraction. To do.
前記多孔質ケイ酸カルシウム水和物粉粒体は、付着水等の貯蔵環境に存在する水分中にゆっくりと溶解し、かかる水を弱アルカリ性（ｐＨ８～ｐＨ１０）に変化させる。この多孔質ケイ酸カルシウム水和物粉粒体による弱アルカリ環境の生成によって、パーム椰子種子殻からの不快臭の発生が抑制される。
The porous calcium silicate hydrate powder or granular material slowly dissolves in water existing in a storage environment such as adhering water, and changes the water to be weakly alkaline (pH 8 to pH 10). The generation of a weak alkaline environment by the porous calcium silicate hydrate powder granules suppresses the generation of an unpleasant odor from palm coconut seed husks.
例えば、パーム椰子種子殻の主要な不快臭であるカルボン酸類からの酸味臭は、パーム椰子種子殻をｐＨ８以上のアルカリ水と接触させることによる化学的中和反応によって、効果的に抑制できる。
For example, the sour odor from carboxylic acids, which is the main unpleasant odor of palm coconut seed husks, can be effectively suppressed by a chemical neutralization reaction by contacting the palm coconut seed husks with alkaline water having a pH of 8 or higher.
更に、パーム椰子種子殻の貯蔵時には、パーム椰子種子殻中の炭水化物等の加水分解によってメタン発酵が進行する環境が形成され、パーム椰子種子殻にアンモニア態窒素（「アンモニア性窒素」とも称される。）が生じ得る。このアンモニア態窒素は、アルカリ性溶液と触れると、アンモニアとして揮発して特有の刺激臭を発生する。このアンモニア態窒素の揮散は、溶液のアルカリ度が高いほど短時間に多量に生じるため、多孔質ケイ酸カルシウム水和物粉粒体が形成する弱アルカリ性環境下（ｐＨ８～１０）であれば、かかるアンモニアの揮発も有効に抑制することができる。
Furthermore, when the palm coconut seed husks are stored, an environment is formed in which methane fermentation proceeds by hydrolysis of carbohydrates in the palm coconut husks, and ammonia nitrogen (also referred to as "ammoniae nitrogen") is formed in the palm coconut seed husks. .) Can occur. When this ammonia nitrogen comes into contact with an alkaline solution, it volatilizes as ammonia and generates a peculiar pungent odor. This volatilization of ammonia nitrogen occurs in a large amount in a short time as the alkalinity of the solution increases. Therefore, in a weak alkaline environment (pH 8 to 10) formed by porous calcium silicate hydrate powder or granular material, Such volatilization of ammonia can also be effectively suppressed.
前記多孔質ケイ酸カルシウム水和物粉粒体は、トバモライト（Ｃａ5（Ｓｉ6Ｏ18Ｈ2）・ｎＨ2Ｏ）を主要構成相とする多孔質体であり、５０ｍ2／ｇ～８０ｍ2／ｇの比表面積を有するものとしても構わない。
The porous calcium silicate hydrate powder or granular material is a porous body having tovamorite (Ca 5 (Si 6 O 18 H 2 ), nH 2 O) as a main constituent phase, and is 50 m 2 / g to 80 m 2 It may have a specific surface area of / g.
上記のような、比表面積の高い多孔質ケイ酸カルシウム水和物粉粒体によれば、臭気成分の吸着能が実現される。例えば、アンモニアガスについては、多孔質ケイ酸カルシウム水和物粉粒体１ｇあたり５００μＬ以上を吸着することができる。このため、かかる多孔質ケイ酸カルシウム水和物粉粒体を、パーム椰子種子殻に混合することで、化学的中和反応に加えて、多孔質ケイ酸カルシウム水和物粉粒体自体が有する吸着能により、不快臭の低減効果が更に高められる。
According to the porous calcium silicate hydrate powder or granular material having a high specific surface area as described above, the ability to adsorb odorous components is realized. For example, with respect to ammonia gas, 500 μL or more can be adsorbed per 1 g of porous calcium silicate hydrate powder or granular material. Therefore, by mixing the porous calcium silicate hydrate powder or granular material with the palm coconut seed shell, in addition to the chemical neutralization reaction, the porous calcium silicate hydrate powder or granular material itself has. The adsorptive capacity further enhances the effect of reducing unpleasant odors.
前記多孔質ケイ酸カルシウム水和物粉粒体は、空隙率が６０体積％～８０体積％、かさ比重が０．８ｇ／ｍＬ以下であるものとしても構わない。
The porous calcium silicate hydrate powder or granular material may have a porosity of 60% by volume to 80% by volume and a bulk specific gravity of 0.8 g / mL or less.
多孔質ケイ酸カルシウム水和物粉粒体の空隙率が６０体積％未満であると、貯蔵環境に存在する水分を多孔質ケイ酸カルシウム水和物粉粒体内に取り込む効果が充分に得られない可能性があると共に、上記の不快臭成分の吸着能が低下する。一方で、空隙率が８０体積％を超える程度に空隙が多く存在すると、パーム椰子種子殻と混合した際に多孔質ケイ酸カルシウム水和物粉粒体が壊れて微粒子化するという問題が生じる可能性がある。
If the porosity of the porous calcium silicate hydrate powder or granular material is less than 60% by volume, the effect of taking in the water existing in the storage environment into the porous calcium silicate hydrate powder or granular material cannot be sufficiently obtained. In addition to the possibility, the ability to adsorb the above-mentioned unpleasant odor components is reduced. On the other hand, if there are many voids so that the porosity exceeds 80% by volume, there may be a problem that the porous calcium silicate hydrate powder granules are broken into fine particles when mixed with palm coconut seed husks. There is sex.
また、多孔質ケイ酸カルシウム水和物粉粒体のかさ比重が大きすぎることは、上記の空隙率の減少と同様に、貯蔵環境に存在する水分を多孔質ケイ酸カルシウム水和物粉粒体内に取り込む効果が充分に得られない可能性があると共に、上記の不快臭成分の吸着能が低下するという問題が生じる可能性があるため、０．８ｇ／ｍＬ以下とするのが好ましい。
In addition, if the bulk specific gravity of the porous calcium silicate hydrate powder or granular material is too large, the water existing in the storage environment is removed from the porous calcium silicate hydrate powder or granular material in the same manner as the above-mentioned decrease in porosity. It is preferable that the amount is 0.8 g / mL or less because the effect of incorporating the unpleasant odor component may not be sufficiently obtained and the problem of lowering the adsorption ability of the above-mentioned unpleasant odor component may occur.
本発明の処理方法によれば、熱源を必要とすることなく、パーム椰子種子殻の不快臭の発生を抑制することが可能となる。
According to the treatment method of the present invention, it is possible to suppress the generation of an unpleasant odor of palm coconut seed husks without the need for a heat source.
核油を搾取して得られるパーム椰子種子殻は、通常、約３０質量％の高い含水率を有している。かかるパーム椰子種子殻は、野積みされたヤードから船舶等に積み込まれて輸送されるのが一般的であり、その際の含水率は、天日で乾燥されたとしても、その表面部で１７質量％程度であり、内部に至っては２０質量％を超える。そして、かかる含水率を有するパーム椰子種子殻は、陸揚げ時や貯蔵時において不快臭による臭気問題が生じる場合がある。
Palm coconut seed husks obtained by exploiting nuclear oil usually have a high water content of about 30% by mass. Such palm coconut seed husks are generally loaded onto a ship or the like from an open-loaded yard and transported, and the water content at that time is 17 on the surface thereof even if it is dried in the sun. It is about mass%, and exceeds 20 mass% inside. Then, the palm coconut seed husk having such a water content may cause an odor problem due to an unpleasant odor at the time of landing or storage.
パーム椰子種子殻から発生する臭気成分には、アルデヒド類、カルボン酸類、エステル類、ケトン類、チオール類等が含まれており、中でもアルデヒド類及びカルボン酸類が、不快臭に関する主要な臭気成分である。
Odor components generated from palm coconut seed husks include aldehydes, carboxylic acids, esters, ketones, thiols, etc. Among them, aldehydes and carboxylic acids are the main odor components related to unpleasant odors. ..
本発明に係る方法は、このように不快臭が発生し得るパーム椰子種子殻に、多孔質ケイ酸カルシウム水和物粉粒体を混合する工程（ａ）を有することを特徴とするものであり、かかる工程（ａ）によって、不快臭を低減する効果が奏される。この点については、実施例を参照して後述される。
The method according to the present invention is characterized by having a step (a) of mixing porous calcium silicate hydrate powder or granular material with palm coconut seed husks which may generate an unpleasant odor. By the step (a), the effect of reducing the unpleasant odor is achieved. This point will be described later with reference to Examples.
工程（ａ）で用いられる多孔質ケイ酸カルシウム水和物粉粒体は、例えば、珪石等のケイ素源（ＳｉＯ2）、石灰等のカルシウム源（ＣａＯ）、及び水を主原料に、高温・高圧下の圧力容器内における水熱反応によって製造されたものや、セメントペースト硬化体等の、骨材含有量の少ないセメント硬化体が利用できる。好ましくは、空隙率（「細孔率」とも称される。）が６０体積％～８０体積％、かさ比重が０．８ｇ／ｍＬ以下の多孔質軽量粉粒体である。なお、本発明における多孔質ケイ酸カルシウム水和物粉粒体の空隙率は、水銀圧入式ポロシメーターによる測定値であり、多孔質ケイ酸カルシウム水和物粉粒体のかさ比重は、ＪＩＳ Ａ ５４３０「繊維強化セメント板」のけい酸カルシウム板に係る手順に準じた方法による測定値である。
The porous calcium silicate hydrate powder or granular material used in the step (a) uses, for example, a silicon source (SiO 2 ) such as silica stone, a calcium source (CaO) such as lime, and water as main raw materials at a high temperature. A cement-hardened material having a low aggregate content, such as a product produced by a hydrothermal reaction in a pressure vessel under high pressure or a cement paste-hardened material, can be used. Preferably, it is a porous lightweight powder or granular material having a porosity (also referred to as “porosity”) of 60% by volume to 80% by volume and a bulk specific gravity of 0.8 g / mL or less. The porosity of the porous calcium silicate hydrate powder or granular material in the present invention is a value measured by a mercury press-fitting porosimeter, and the bulk specific gravity of the porous calcium silicate hydrate powder or granular material is JIS A 5430. It is a measured value by the method according to the procedure concerning the calcium silicate board of "fiber reinforced cement board".
工程（ａ）で用いられる多孔質ケイ酸カルシウム水和物粉粒体の大きさは、例えば水熱反応で得られた多孔質ケイ酸カルシウム水和物硬化体を、粉砕、分級することで任意の大きさに調整することが可能である。ただし、後述する、使用後の多孔質ケイ酸カルシウム水和物粉粒体を再利用するための回収を容易に行う観点から、大きさが数ｃｍのパーム椰子種子殻に対して、層別可能な大きさである５ｍｍ以下の多孔質ケイ酸カルシウム水和物粉粒体であるのが好ましい。すなわち、工程（ａ）で用いられる多孔質ケイ酸カルシウム水和物粉粒体は、粒径５ｍｍ以下であるのが好ましい。
The size of the porous calcium silicate hydrate powder or granular material used in the step (a) is arbitrary by, for example, crushing and classifying the cured porous calcium silicate hydrate obtained by a hydrothermal reaction. It is possible to adjust the size of. However, from the viewpoint of facilitating recovery for reusing the porous calcium silicate hydrate powder and granules after use, which will be described later, stratification is possible for palm coconut seed husks having a size of several cm. It is preferably a porous calcium silicate hydrate powder or granular material having a large size of 5 mm or less. That is, the porous calcium silicate hydrate powder or granular material used in the step (a) preferably has a particle size of 5 mm or less.
なお、本発明における多孔質ケイ酸カルシウム水和物粉粒体の粒径は、多孔質ケイ酸カルシウム水和物粉粒体が通過可能な網篩（ふるい）の内、最小の篩目の大きさを指す。
The particle size of the porous calcium silicate hydrate powder or granular material in the present invention is the smallest mesh size among the mesh sieves (sieves) through which the porous calcium silicate hydrate powder or granular material can pass. Refers to.
工程（ａ）で用いられる多孔質ケイ酸カルシウム水和物粉粒体は、パーム椰子種子殻の消臭用として製造されたものであっても構わないが、上記の特徴を有するものであれば、例えば、水質・底質浄化材や軽量気泡コンクリート等、他の用途向けに製造された物を流用しても構わない。後者の場合、本発明の処理方法は、軽量気泡コンクリートの製造で発生する端材等の有効な活用方法を提供することにもつながる。
The porous calcium silicate hydrate powder or granular material used in the step (a) may be produced for deodorizing palm coconut seed husks, as long as it has the above characteristics. For example, a product manufactured for other purposes such as a water quality / bottom sediment purification material or a lightweight cellular concrete may be diverted. In the latter case, the treatment method of the present invention also leads to providing an effective utilization method of scraps and the like generated in the production of lightweight aerated concrete.
パーム椰子種子殻の貯蔵空間内の雰囲気には、通常、一定量の水分が存在する。このため、工程（ａ）において、パーム椰子種子殻に多孔質ケイ酸カルシウム水和物粉粒体を混合することで、多孔質ケイ酸カルシウム水和物粉粒体が水に対してゆっくりと溶解し、かかる水を弱アルカリ性（ｐＨ８～１０）に変化させる。この結果、パーム椰子種子殻から発生する臭気成分として上述したアルデヒド類やカルボン酸類等に対する化学的中和反応が生じ、不快臭が低減される。
A certain amount of water is usually present in the atmosphere inside the storage space of palm coconut seed husks. Therefore, in step (a), by mixing the porous calcium silicate hydrate powder and granules with the palm coconut seed shell, the porous calcium silicate hydrate powder and granules are slowly dissolved in water. Then, the water is changed to weakly alkaline (pH 8 to 10). As a result, a chemical neutralization reaction with the above-mentioned aldehydes, carboxylic acids and the like as an odor component generated from palm coconut seed husks occurs, and an unpleasant odor is reduced.
雰囲気内に載置された多孔質ケイ酸カルシウム水和物粉粒体の細孔内には雰囲気由来の細孔水が常に存在し、また細孔以外の表面部にも雰囲気由来の吸着水が存在し、それらの水にケイ酸カルシウム水和物が常に溶解するため、多孔質ケイ酸カルシウム水和物粉粒体の表面はｐＨ１０前後の弱アルカリ性を保持している。従って、工程（ａ）で用いられる多孔質ケイ酸カルシウム水和物粉粒体は、実施に際して特段の前処理を必要としない。しかしながら、上記の化学的中和反応を更に効果的に生じさせるために、多孔質ケイ酸カルシウム水和物粉粒体に対して予め水濡れさせて含水率を高めた状態にして工程（ａ）で利用されるものとしても構わない。
Pore water derived from the atmosphere is always present in the pores of the porous calcium silicate hydrate powder and granules placed in the atmosphere, and adsorbed water derived from the atmosphere is also present on the surface other than the pores. Since it is present and calcium silicate hydrate is always dissolved in those waters, the surface of the porous calcium silicate hydrate powder and granules retains weak alkalinity at around pH 10. Therefore, the porous calcium silicate hydrate powder or granular material used in the step (a) does not require any special pretreatment for implementation. However, in order to more effectively cause the above-mentioned chemical neutralization reaction, the porous calcium silicate hydrate powder or granular material is previously wetted with water to increase the water content in the step (a). It does not matter if it is used in.
このように、工程（ａ）で利用される多孔質ケイ酸カルシウム水和物粉粒体の含水率が高い場合、高アルカリ環境下でパーム椰子種子殻から揮散するアンモニアが、かかる水分中に溶解するため、不快臭として感得されるアンモニアを低減する効果も得られる。
As described above, when the water content of the porous calcium silicate hydrate powder or granular material used in the step (a) is high, the ammonia volatilized from the palm coconut seed shell in a highly alkaline environment dissolves in the water. Therefore, the effect of reducing ammonia perceived as an unpleasant odor can also be obtained.
多孔質ケイ酸カルシウム水和物粉粒体の含水率を高める方法としては、特に制限はなく、散水や、水に浸漬するなどの常用の方法を用いればよい。ただし、過剰な含水率は、かかる水のアルカリ度を迅速に高めることが困難であるとともに、パーム椰子種子殻の腐敗を促進させてしまう場合もあるため、含水率は６０質量％以下とするのが好ましく、より好ましくは３０質量％以上、５０質量％以下である。ここで、多孔質ケイ酸カルシウム水和物粉粒体の含水率の測定方法は、例えば、ＪＩＳ Ａ １１２５「骨材の含水率試験方法及び含水率に基づく表面水率の試験方法」記載の試験方法、すなわち１０５±５℃の乾燥温度で恒量となった前後の多孔質ケイ酸カルシウム水和物粉粒体の質量から求めることができる。
The method for increasing the water content of the porous calcium silicate hydrate powder or granular material is not particularly limited, and a usual method such as sprinkling water or immersing in water may be used. However, the excessive water content makes it difficult to quickly increase the alkalinity of the water and may promote the decay of palm coconut seed husks. Therefore, the water content should be 60% by mass or less. Is preferable, and more preferably 30% by mass or more and 50% by mass or less. Here, the method for measuring the water content of the porous calcium silicate hydrate powder or granular material is, for example, the test described in JIS A1125 “Aggregate water content test method and surface water content test method based on water content”. It can be obtained from the method, that is, the mass of the porous calcium silicate hydrate powder or granular material before and after becoming constant at a drying temperature of 105 ± 5 ° C.
パーム椰子種子殻と多孔質ケイ酸カルシウム水和物粉粒体を混合する方法は、両者が良好に混合できる方法であれば特に制限はない。例えば、粉粒体の混合装置を用いた混合、重機による混合、ベルトコンベア等の搬送装置での混載など、粉粒体の混合における常用の方法を利用することができる。
The method of mixing the palm coconut seed husk and the porous calcium silicate hydrate powder or granular material is not particularly limited as long as both can be mixed well. For example, a common method for mixing powders and granules can be used, such as mixing using a powder or granular material mixing device, mixing with a heavy machine, or mixing with a transport device such as a belt conveyor.
パーム椰子種子殻に対して工程（ａ）に係る混合処理を行うタイミング（時期）は、パーム椰子種子殻が生成されてから、貯蔵され、搬送される迄の間のうちで、時期が限定されるものではない。しかし、不快臭の発生が低度の時期ほど実施するのが好ましいという観点からは、搾油されて生成された直後のパーム椰子種子殻に対して、工程（ａ）に係る混合処理を実行するのが好ましい。すなわち、工程（ａ）に係る混合処理は、パーム椰子種子殻の供給地で行われることが、最も好ましい。
The timing (timing) of performing the mixing treatment according to the step (a) on the palm coconut seed husks is limited from the time when the palm coconut seed husks are produced to the time when they are stored and transported. It's not something. However, from the viewpoint that it is preferable to carry out the process when the generation of unpleasant odor is low, the mixing treatment according to the step (a) is carried out on the palm coconut seed husks immediately after being squeezed and produced. Is preferable. That is, it is most preferable that the mixing treatment according to the step (a) is performed at the palm coconut seed husk supply area.
工程（ａ）に係る混合処理で利用される多孔質ケイ酸カルシウム水和物粉粒体の量（混合量）は、混合処理後に得られるパーム椰子種子殻と多孔質ケイ酸カルシウム水和物粉粒体の混合物１００質量部に対し、２質量部～５０質量部であるのが好ましく、５質量部～５０質量部であるのがより好ましく、５質量部～２５質量部であるのが特に好ましい。
The amount (mixing amount) of the porous calcium silicate hydrate powder granules used in the mixing treatment according to the step (a) is the palm coconut seed husk and the porous calcium silicate hydrate powder obtained after the mixing treatment. It is preferably 2 parts by mass to 50 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and particularly preferably 5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the mixture of granules. ..
工程（ａ）で利用される多孔質ケイ酸カルシウム水和物粉粒体の量が、混合物１００質量部に対して２質量部未満である場合には、不快臭を低下させる効果が充分に得られない可能性がある。一方、工程（ａ）で利用される多孔質ケイ酸カルシウム水和物粉粒体の量が、混合物１００質量部に対して５０質量部を超える場合には、混合物に占めるパーム椰子種子殻の割合が少ないという問題が生じる可能性がある。
When the amount of the porous calcium silicate hydrate powder or granular material used in the step (a) is less than 2 parts by mass with respect to 100 parts by mass of the mixture, the effect of reducing the unpleasant odor is sufficiently obtained. It may not be possible. On the other hand, when the amount of the porous calcium silicate hydrate powder or granular material used in the step (a) exceeds 50 parts by mass with respect to 100 parts by mass of the mixture, the ratio of palm coconut seed husks to the mixture. May cause the problem of low levels.
なお、混合処理において利用される多孔質ケイ酸カルシウム水和物粉粒体が上述した事前の含水処理が施されている場合、混合処理で利用される多孔質ケイ酸カルシウム水和物粉粒体の量には、上記の含水処理による水分量を含むものとして構わない。
When the porous calcium silicate hydrate powder or granular material used in the mixing treatment is subjected to the above-mentioned prior water-containing treatment, the porous calcium silicate hydrate powder or granular material used in the mixing treatment is applied. The amount of water may include the amount of water due to the above water content treatment.
多孔質ケイ酸カルシウム水和物粉粒体が混合されたパーム椰子種子殻は、そのまま燃料として用いることも可能であるが、多孔質ケイ酸カルシウム水和物粉粒体を含有することによって燃料としての特性が変化することが予想される。また、混合後に残留する多孔質ケイ酸カルシウム水和物粉粒体は、依然として、消臭効果を継続して有しているので再利用することが可能である。これらの観点から、工程（ａ）を実行後、燃料として使用する前段階において、パーム椰子種子殻と多孔質ケイ酸カルシウム水和物粉粒体の混合物から、多孔質ケイ酸カルシウム水和物粉粒体を分離、回収するのが好ましい。
Palm coconut seed husks mixed with porous calcium silicate hydrate powder and granules can be used as fuel as they are, but by containing porous calcium silicate hydrate powder and granules, they can be used as fuel. It is expected that the characteristics of will change. Further, the porous calcium silicate hydrate powder or granular material remaining after mixing still has a deodorizing effect and can be reused. From these points of view, after performing step (a), in the pre-stage of use as fuel, from a mixture of palm coconut seed husk and porous calcium silicate hydrate powder granules, porous calcium silicate hydrate powder It is preferable to separate and recover the granules.
混合物から多孔質ケイ酸カルシウム水和物粉粒体を回収するに際しては、例えば目開きが６ｍｍ～９ｍｍの篩を用い、この篩を通過した多孔質ケイ酸カルシウム水和物粉粒体を回収することができる。また、かかる篩通過分に混入しているパーム椰子種子殻由来のファイバーなどは、当該篩通過分を風力選別することで、分離回収が可能である。この回収された多孔質ケイ酸カルシウム水和物粉粒体は、再び工程（ａ）に係る混合処理に利用されるものとしても構わない。
When recovering the porous calcium silicate hydrate powder or granular material from the mixture, for example, a sieve having a mesh size of 6 mm to 9 mm is used, and the porous calcium silicate hydrate powder or granular material that has passed through this sieve is recovered. be able to. In addition, fibers derived from palm coconut seed husks mixed in the sieve-passed portion can be separated and recovered by wind-sorting the sieve-passed portion. The recovered porous calcium silicate hydrate powder or granular material may be used again for the mixing treatment according to the step (a).
なお、多孔質ケイ酸カルシウム水和物粉粒体は、ボイラー等でパーム椰子種子殻と共に燃焼された場合、脱硫剤として硫黄酸化物を固定する能力を有している。このため、工程（ａ）が完了後、残存する多孔質ケイ酸カルシウム水和物粉粒体の全てを除去することなく、一部の多孔質ケイ酸カルシウム水和物粉粒体を意図的に残したまま燃料として利用しても構わない。
The porous calcium silicate hydrate powder granules have the ability to fix sulfur oxides as a desulfurizing agent when burned together with palm coconut seed husks in a boiler or the like. Therefore, after the step (a) is completed, some of the porous calcium silicate hydrate powders and granules are intentionally removed without removing all of the remaining porous calcium silicate hydrate powders and granules. You may use it as fuel while leaving it.
以下、本発明に係る処理方法につき、実施例を参照して更に具体的に説明する。ただし、本発明は、かかる実施例に限定されるものではない。
Hereinafter, the processing method according to the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to such examples.
以下の実施例において、臭気の評価、及び多孔質ケイ酸カルシウム水和物粉粒体の含水率の評価は、以下のようにして行った。
In the following examples, the odor was evaluated and the water content of the porous calcium silicate hydrate powder was evaluated as follows.
《１》臭気の評価
容積２Ｌのポリエチレン製広口瓶内に試料を封入し、蓋をしていない状態で、２５±５℃の屋内に静置した。その後、蓋をして密閉した状態とし、３０℃の恒温槽に３０分間静置した。 << 1 >> Evaluation of odor A sample was sealed in a polyethylene wide-mouthed bottle having a volume of 2 L, and the sample was allowed to stand indoors at 25 ± 5 ° C. without a lid. Then, the lid was closed and the mixture was kept in a constant temperature bath at 30 ° C. for 30 minutes.
容積２Ｌのポリエチレン製広口瓶内に試料を封入し、蓋をしていない状態で、２５±５℃の屋内に静置した。その後、蓋をして密閉した状態とし、３０℃の恒温槽に３０分間静置した。 << 1 >> Evaluation of odor A sample was sealed in a polyethylene wide-mouthed bottle having a volume of 2 L, and the sample was allowed to stand indoors at 25 ± 5 ° C. without a lid. Then, the lid was closed and the mixture was kept in a constant temperature bath at 30 ° C. for 30 minutes.
その後、広口瓶のヘッドスペースに発生した臭気成分について、臭気の総合的な定量的計測としてにおいセンサー（新コスモス電機株式会社製ＸＰ?３２９ＩＩＩＲ）による測定と、特定臭気としてカルボン酸とアンモニアの２成分について、検知管（カルボン酸：株式会社ガステック製８１Ｌ、アンモニア：光明理化学工業株式会社製１０５ＳＥ）による測定を行った。
After that, the odor components generated in the head space of the wide-mouthed bottle were measured by an odor sensor (XP? 329IIIR manufactured by New Cosmos Electric Co., Ltd.) as a comprehensive quantitative measurement of the odor, and two components of carboxylic acid and ammonia as specific odors. Was measured with a detector tube (carboxylic acid: 81L manufactured by Gastec Co., Ltd., ammonia: 105SE manufactured by Komei Rikagaku Kogyo Co., Ltd.).
なお、前記の測定は、広口瓶に試料を封入してから１日後、４日後、７日後、１０日後の各日に行われた。
The above measurement was performed on each day 1 day, 4 days, 7 days, and 10 days after the sample was sealed in the wide-mouthed bottle.
《２》多孔質ケイ酸カルシウム水和物粉粒体の含水率の算出
含水処理などが施された多孔質ケイ酸カルシウム水和物粉粒体について、１０５℃の乾燥温度で恒量となった際の、乾燥前質量（Ｗ１）と乾燥後質量（Ｗ２）を測定し、下記の式（１）により含水率を算出した。
含水率（質量％）＝（（Ｗ１－Ｗ２）／Ｗ２）×１００ ・・・（１） << 2 >> Calculation of Moisture Content of Porous Calcium Silica Hydrate Powder Granules When the amount of porous calcium silicate hydrate powder granules subjected to water content treatment becomes constant at a drying temperature of 105 ° C. The mass before drying (W1) and the mass after drying (W2) were measured, and the water content was calculated by the following formula (1).
Moisture content (mass%) = ((W1-W2) / W2) x 100 ... (1)
含水処理などが施された多孔質ケイ酸カルシウム水和物粉粒体について、１０５℃の乾燥温度で恒量となった際の、乾燥前質量（Ｗ１）と乾燥後質量（Ｗ２）を測定し、下記の式（１）により含水率を算出した。
含水率（質量％）＝（（Ｗ１－Ｗ２）／Ｗ２）×１００ ・・・（１） << 2 >> Calculation of Moisture Content of Porous Calcium Silica Hydrate Powder Granules When the amount of porous calcium silicate hydrate powder granules subjected to water content treatment becomes constant at a drying temperature of 105 ° C. The mass before drying (W1) and the mass after drying (W2) were measured, and the water content was calculated by the following formula (1).
Moisture content (mass%) = ((W1-W2) / W2) x 100 ... (1)
使用した材料は以下の通りである。
・パーム椰子種子殻：Ｔｅｎｅｒａ種の種子殻（マレーシア産）。搾油処理後２週間以上経過したものを日本国内で採取した。長径約２５ｍｍ×短径約１０ｍｍの楕円形状を呈していた。
・多孔質ケイ酸カルシウム水和物粉粒体：太平洋セメント株式会社製「セラクリーン」（登録商標）。粒径１ｍｍ～４ｍｍの白色顆粒であり、かさ比重が０．４１ｇ／ｍＬ、比表面積７７ｍ2／ｇ、空隙率が６７体積％であった。
・水：上水道水（千葉県佐倉市）
・消石灰：粉末。２倍量の水と混合して得られた粉粒体の表面のｐＨは１２．５であった。 The materials used are as follows.
-Palm palm seed husks: Tenera seed husks (made in Malaysia). Those 2 weeks or more after the oil squeezing treatment were collected in Japan. It had an elliptical shape with a major axis of about 25 mm and a minor axis of about 10 mm.
-Porous calcium silicate hydrate powder granules: "Ceraclean" (registered trademark) manufactured by Taiheiyo Cement Co., Ltd. The white granules had a particle size of 1 mm to 4 mm, a bulk specific gravity of 0.41 g / mL, a specific surface area of 77 m 2 / g, and a porosity of 67% by volume.
・ Water: Tap water (Sakura City, Chiba Prefecture)
-Slaked lime: powder. The pH of the surface of the powder or granular material obtained by mixing with twice the amount of water was 12.5.
・パーム椰子種子殻：Ｔｅｎｅｒａ種の種子殻（マレーシア産）。搾油処理後２週間以上経過したものを日本国内で採取した。長径約２５ｍｍ×短径約１０ｍｍの楕円形状を呈していた。
・多孔質ケイ酸カルシウム水和物粉粒体：太平洋セメント株式会社製「セラクリーン」（登録商標）。粒径１ｍｍ～４ｍｍの白色顆粒であり、かさ比重が０．４１ｇ／ｍＬ、比表面積７７ｍ2／ｇ、空隙率が６７体積％であった。
・水：上水道水（千葉県佐倉市）
・消石灰：粉末。２倍量の水と混合して得られた粉粒体の表面のｐＨは１２．５であった。 The materials used are as follows.
-Palm palm seed husks: Tenera seed husks (made in Malaysia). Those 2 weeks or more after the oil squeezing treatment were collected in Japan. It had an elliptical shape with a major axis of about 25 mm and a minor axis of about 10 mm.
-Porous calcium silicate hydrate powder granules: "Ceraclean" (registered trademark) manufactured by Taiheiyo Cement Co., Ltd. The white granules had a particle size of 1 mm to 4 mm, a bulk specific gravity of 0.41 g / mL, a specific surface area of 77 m 2 / g, and a porosity of 67% by volume.
・ Water: Tap water (Sakura City, Chiba Prefecture)
-Slaked lime: powder. The pH of the surface of the powder or granular material obtained by mixing with twice the amount of water was 12.5.
測定対象とされた各水準は、以下の表１の通りである。なお、各水準において、臭気の発生源となるパーム椰子種子殻の量を一定（８００ｇ）にするため、多孔質ケイ酸カルシウム水和物粉粒体、及び含水消石灰を混合する際には、外割混合した。
Table 1 below shows each level to be measured. In addition, in order to keep the amount of palm coconut seed husks, which are the source of odor, constant (800 g) at each level, when mixing porous calcium silicate hydrate powder and granules and hydrous slaked lime, the outside is used. It was split and mixed.
水準１は、多孔質ケイ酸カルシウム水和物粉粒体をパーム椰子種子殻に混合しなかった場合であり、比較例に対応する。
Level 1 is the case where the porous calcium silicate hydrate powder and granules are not mixed with the palm coconut seed husk, which corresponds to a comparative example.
水準２は、２倍量の水と練り混ぜて得られた消石灰粉粒体をパーム椰子種子殻に混合した場合であり、比較例に対応する。
Level 2 is a case where slaked lime powder granules obtained by kneading with twice the amount of water are mixed with palm coconut seed husks, which corresponds to a comparative example.
水準３～５は、含水率を０質量％とした多孔質ケイ酸カルシウム水和物粉粒体を、それぞれ混合量を異ならせた状態でパーム椰子種子殻に対して混合した場合に対応する。また、水準５～７は、それぞれ含水率の異なる多孔質ケイ酸カルシウム水和物粉粒体を、混合量を一定にした状態でパーム椰子種子殻に混合した場合に対応する。これらの水準３～７が実施例に対応する。なお、水準５～７において、多孔質ケイ酸カルシウム水和物粉粒体の含水率は、混合前に所定量の水を散布することで調整された。
Levels 3 to 5 correspond to the case where porous calcium silicate hydrate powders and granules having a water content of 0% by mass are mixed with palm coconut seed husks in different mixing amounts. Levels 5 to 7 correspond to the case where porous calcium silicate hydrate powders and granules having different water contents are mixed with palm coconut seed husks in a state where the mixing amount is constant. These levels 3-7 correspond to the examples. At levels 5 to 7, the water content of the porous calcium silicate hydrate powder granules was adjusted by spraying a predetermined amount of water before mixing.
表１に示された、各水準１～７について、臭いの評価を実施した結果を表２に示す。なお表２において、「＞１０」なる記載は、数値が１０より大きかったことを意味しており、「＜０．５」なる記載は、数値が０．５未満であったことを意味しており、「－」なる記載は、測定されていないことを意味している。
Table 2 shows the results of odor evaluation for each level 1 to 7 shown in Table 1. In Table 2, the description "> 10" means that the numerical value was larger than 10, and the description "<0.5" means that the numerical value was less than 0.5. The description "-" means that it has not been measured.
表２によれば、多孔質ケイ酸カルシウム水和物粉粒体を混合しなかった水準１においては、日数が経過してもなお、高い臭気が示されていることが分かる。また、アンモニア検知管では検知できなかった一方で、カルボン酸検知管では高い数値が確認されていることから、この臭気の原因の一つがパーム椰子種子殻由来のカルボン酸であることが分かる。
According to Table 2, it can be seen that at level 1 in which the porous calcium silicate hydrate powder or granular material was not mixed, a high odor was still exhibited even after the lapse of days. In addition, while the ammonia detector tube could not detect it, a high value was confirmed in the carboxylic acid detector tube, indicating that one of the causes of this odor is the carboxylic acid derived from palm coconut seed husks.
ｐＨが１２を超える水準２においては、カルボン酸の臭気は充分に抑制できているが、日数が経過してもなお、多量のアンモニアが生じていたことが分かる。このことから、過剰なアルカリ環境では、不快臭の発生を抑制できないことが分かる。
At level 2 where the pH exceeds 12, the odor of the carboxylic acid can be sufficiently suppressed, but it can be seen that a large amount of ammonia was still generated even after the lapse of days. From this, it can be seen that the generation of unpleasant odor cannot be suppressed in an excessive alkaline environment.
一方、多孔質ケイ酸カルシウム水和物粉粒体を混合した水準３～７によれば、いずれも水準１と比べて、においセンサーの指示値、カルボン酸検知管の検知値が低いことが分かる。また、水準３～７によれば、水準２と比べて、アンモニア検知管の検知値が低いことが分かる。つまり、多孔質ケイ酸カルシウム水和物粉粒体を混合することで、アルカリによるアンモニアの揮散はほとんど生じない状態において、不快臭の主要成分であるカルボン酸の揮散を充分に抑制できることが分かる。
On the other hand, according to Levels 3 to 7 in which porous calcium silicate hydrate powders and granules are mixed, it can be seen that the indicated values of the odor sensor and the detected values of the carboxylic acid detector tube are lower than those of Level 1. .. Further, according to the levels 3 to 7, it can be seen that the detection value of the ammonia detector tube is lower than that of the level 2. That is, it can be seen that by mixing the porous calcium silicate hydrate powder or granular material, the volatilization of carboxylic acid, which is a main component of an unpleasant odor, can be sufficiently suppressed in a state where the volatilization of ammonia by alkali hardly occurs.
なお、混合される多孔質ケイ酸カルシウム水和物粉粒体の含水率を異ならせた水準５～７に関して、表２によれば、含水率の高い水準７、水準６、水準５の順に、カルボン酸検知管の検知値が低下していることが分かる。これにより、多孔質ケイ酸カルシウム水和物粉粒体の含水率が５０質量％以下の範囲内においては、含水率を高めるほど、不快臭の主要成分であるカルボン酸の揮散を抑制する効果が高められることが分かる。
Regarding levels 5 to 7 in which the water contents of the mixed porous calcium silicate hydrate powders and granules were different, according to Table 2, the water contents were higher in the order of level 7, level 6, and level 5. It can be seen that the detection value of the carboxylic acid detector tube is decreasing. As a result, when the water content of the porous calcium silicate powder or granular material is within the range of 50% by mass or less, the higher the water content, the more effective the effect of suppressing the volatilization of carboxylic acid, which is the main component of the unpleasant odor. You can see that it can be enhanced.
Regarding levels 5 to 7 in which the water contents of the mixed porous calcium silicate hydrate powders and granules were different, according to Table 2, the water contents were higher in the order of level 7, level 6, and level 5. It can be seen that the detection value of the carboxylic acid detector tube is decreasing. As a result, when the water content of the porous calcium silicate powder or granular material is within the range of 50% by mass or less, the higher the water content, the more effective the effect of suppressing the volatilization of carboxylic acid, which is the main component of the unpleasant odor. You can see that it can be enhanced.
Claims (8)
- パーム椰子種子殻に、多孔質ケイ酸カルシウム水和物粉粒体を混合する工程（ａ）を有することを特徴とする、パーム椰子種子殻の処理方法。 A method for treating palm coconut seed husks, which comprises a step (a) of mixing porous calcium silicate hydrate powders and granules with palm coconut seed husks.
- 前記多孔質ケイ酸カルシウム水和物粉粒体が、トバモライトを主要構成相とし、比表面積が５０ｍ２／ｇ～８０ｍ２／ｇであることを特徴とする、請求項１に記載のパーム椰子種子殻の処理方法。 The palm coconut seed according to claim 1, wherein the porous calcium silicate hydrate powder or granular material contains tovamorite as a main constituent phase and has a specific surface area of 50 m 2 / g to 80 m 2 / g. How to handle the shell.
- 前記多孔質ケイ酸カルシウム水和物粉粒体は、空隙率が６０体積％～８０体積％、かさ比重が０．８ｇ／ｍＬ以下であることを特徴とする、請求項１又は２に記載のパーム椰子種子殻の処理方法。 The porous calcium silicate powder or granular material according to claim 1 or 2, wherein the porous calcium silicate powder or granular material has a porosity of 60% by volume to 80% by volume and a bulk specific weight of 0.8 g / mL or less. How to treat palm coconut seed husks.
- 前記多孔質ケイ酸カルシウム水和物粉粒体は、ケイ素源、カルシウム源、及び水を主原料として水熱反応が施されて得られたものであることを特徴とする、請求項１～３のいずれか１項に記載のパーム椰子種子殻の処理方法。 Claims 1 to 3 are characterized in that the porous calcium silicate hydrate powder or granular material is obtained by subjecting a hydrothermal reaction using a silicon source, a calcium source, and water as main raw materials. The method for treating palm coconut seed husks according to any one of the above.
- 前記多孔質ケイ酸カルシウム水和物粉粒体が、粒径５ｍｍ以下であることを特徴とする、請求項１～４のいずれか１項に記載のパーム椰子種子殻の処理方法。 The method for treating palm coconut seed husks according to any one of claims 1 to 4, wherein the porous calcium silicate hydrate powder or granular material has a particle size of 5 mm or less.
- 前記多孔質ケイ酸カルシウム水和物粉粒体が、６０質量％以下の含水率であることを特徴とする、請求項１～５のいずれか１項に記載のパーム椰子種子殻の処理方法。 The method for treating palm coconut seed husks according to any one of claims 1 to 5, wherein the porous calcium silicate hydrate powder or granular material has a water content of 60% by mass or less.
- 前記工程（ａ）は、前記出荷可能なパーム椰子種子殻と前記多孔質ケイ酸カルシウム水和物粉粒体との混合物１００質量部に対し、２質量部～５０質量部の前記多孔質ケイ酸カルシウム水和物粉粒体を混合する工程であることを特徴とする、請求項１～６のいずれか１項に記載のパーム椰子種子殻の処理方法。 In the step (a), 2 parts by mass to 50 parts by mass of the porous silicate is used with respect to 100 parts by mass of the mixture of the salable palm coconut seed husk and the porous calcium silicate hydrate powder or granular material. The method for treating palm coconut seed husks according to any one of claims 1 to 6, which is a step of mixing calcium hydrate powders and granules.
- 前記多孔質ケイ酸カルシウム水和物粉粒体が再利用品であることを特徴とする、請求項１～７のいずれか１項に記載のパーム椰子種子殻の処理方法。 The method for treating palm coconut seed husks according to any one of claims 1 to 7, wherein the porous calcium silicate hydrate powder or granular material is a recycled product.
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| MYPI2020005578A MY191856A (en) | 2019-09-24 | 2019-09-24 | Method for treating palm kernel shells |
| PCT/JP2019/037317 WO2021059334A1 (en) | 2019-09-24 | 2019-09-24 | Method for treating palm coconut seed husks |
| JP2020519829A JP7002649B2 (en) | 2019-09-24 | 2019-09-24 | How to treat palm palm seed husks |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60180972A (en) * | 1984-02-29 | 1985-09-14 | 小野田エー・エル・シー株式会社 | Manufacture of calcium silicate porous body |
| JPS62212315A (en) * | 1986-03-13 | 1987-09-18 | Agency Of Ind Science & Technol | Powdery deodorant |
| JPH08239675A (en) * | 1995-03-03 | 1996-09-17 | Chichibu Onoda Cement Corp | Preparation of solid fuel from waste and use thereof |
| JP2008504213A (en) * | 2004-06-25 | 2008-02-14 | ジェイ・エム・ヒューバー・コーポレーション | Composition comprising metal oxide silicate to neutralize odor |
| WO2010151101A1 (en) * | 2009-06-26 | 2010-12-29 | Universiti Putra Malaysia | Novel in-vessel high rate composter |
| JP6578077B1 (en) * | 2019-02-13 | 2019-09-18 | 太平洋セメント株式会社 | Biomass fuel distribution method including palm coconut shell, and biomass fuel distribution base including palm coconut shell |
-
2019
- 2019-09-24 JP JP2020519829A patent/JP7002649B2/en active Active
- 2019-09-24 MY MYPI2020005578A patent/MY191856A/en unknown
- 2019-09-24 WO PCT/JP2019/037317 patent/WO2021059334A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60180972A (en) * | 1984-02-29 | 1985-09-14 | 小野田エー・エル・シー株式会社 | Manufacture of calcium silicate porous body |
| JPS62212315A (en) * | 1986-03-13 | 1987-09-18 | Agency Of Ind Science & Technol | Powdery deodorant |
| JPH08239675A (en) * | 1995-03-03 | 1996-09-17 | Chichibu Onoda Cement Corp | Preparation of solid fuel from waste and use thereof |
| JP2008504213A (en) * | 2004-06-25 | 2008-02-14 | ジェイ・エム・ヒューバー・コーポレーション | Composition comprising metal oxide silicate to neutralize odor |
| WO2010151101A1 (en) * | 2009-06-26 | 2010-12-29 | Universiti Putra Malaysia | Novel in-vessel high rate composter |
| JP6578077B1 (en) * | 2019-02-13 | 2019-09-18 | 太平洋セメント株式会社 | Biomass fuel distribution method including palm coconut shell, and biomass fuel distribution base including palm coconut shell |
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| JP7002649B2 (en) | 2022-01-20 |
| MY191856A (en) | 2022-07-18 |
| JPWO2021059334A1 (en) | 2021-10-14 |
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