TWI836414B - Liquid fertilizer manufacturing method - Google Patents
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- TWI836414B TWI836414B TW111116297A TW111116297A TWI836414B TW I836414 B TWI836414 B TW I836414B TW 111116297 A TW111116297 A TW 111116297A TW 111116297 A TW111116297 A TW 111116297A TW I836414 B TWI836414 B TW I836414B
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- sewage sludge
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- 239000007788 liquid Substances 0.000 title claims abstract description 75
- 239000003337 fertilizer Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 65
- 239000011574 phosphorus Substances 0.000 claims abstract description 65
- 239000010801 sewage sludge Substances 0.000 claims abstract description 55
- 238000005470 impregnation Methods 0.000 claims abstract description 53
- 150000007524 organic acids Chemical class 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 229940043430 calcium compound Drugs 0.000 claims abstract description 22
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 7
- 150000003112 potassium compounds Chemical class 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007654 immersion Methods 0.000 claims description 10
- 235000005985 organic acids Nutrition 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 30
- 230000008635 plant growth Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 229910052586 apatite Inorganic materials 0.000 description 21
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 20
- 238000002386 leaching Methods 0.000 description 14
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000011133 lead Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052567 struvite Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009933 burial Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003501 hydroponics Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000013557 nattō Nutrition 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013322 soy milk Nutrition 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Fertilizers (AREA)
Abstract
本發明提供一種液態肥料製造方法，本方法可從下水汙泥製造液態肥料，將下水汙泥與鈣化合物混合後進行熱處理，熱處理後所得之下水汙泥使用混合有機酸進行浸漬處理，經固液分離後，於所得之浸漬液中添加鉀化合物及銨化合物後，製成液態肥料，製成之液態肥料可促進植物生長，且其中之重金屬含量低於我國液態肥料之重金屬含量標準，本方法可達成下水汙泥肥料化，減少磷資源浪費，進而減少下水汙泥的最終處理量。The invention provides a method for manufacturing liquid fertilizer. This method can produce liquid fertilizer from sewage sludge. The sewage sludge is mixed with a calcium compound and then heat-treated. The sewage sludge obtained after heat treatment is impregnated with a mixed organic acid. After separation, potassium compounds and ammonium compounds are added to the obtained impregnation liquid to make liquid fertilizer. The liquid fertilizer can promote plant growth, and the heavy metal content in it is lower than the heavy metal content standard of liquid fertilizer in my country. This method can Fertilize sewage sludge to reduce waste of phosphorus resources, thereby reducing the final disposal volume of sewage sludge.
Description
本發明係有關於液態肥料製造方法，特別係關於一種從下水汙泥製造液態肥料的方法。The present invention relates to a method for manufacturing liquid fertilizer, and in particular to a method for manufacturing liquid fertilizer from sewage sludge.
下水汙泥是生活污水處理的副產物。依據內政部營建署的調查報告，台灣的下水汙泥產生量每年約54,860噸，其中64.4%採取衛生掩埋、15.7%材料化再利用、14.8%焚化處理、5.1%於廠內貯存(汙泥餅)、0.2%肥料化再利用。Sewage sludge is a byproduct of domestic sewage treatment. According to a survey report by the Construction and Planning Agency of the Ministry of the Interior, Taiwan produces about 54,860 tons of sewage sludge each year, of which 64.4% is landfilled, 15.7% is recycled, 14.8% is incinerated, 5.1% is stored in factories (sludge cakes), and 0.2% is recycled as fertilizer.
目前下水汙泥主要的處理方式為衛生掩埋，而台灣地狹人稠，掩埋場址取得不易，下水汙泥的處理逐漸成為問題。At present, the main treatment method for sewage sludge is sanitary burial. However, Taiwan is a small and densely populated land, and it is difficult to obtain a burial site. The treatment of sewage sludge has gradually become a problem.
另一方面，下水汙泥中含有數%的磷，磷是肥料的主要成分元素之一，其磷含量如以10% P 2O 5估算，則台灣每年約有5,486噸的磷資源，相當於每年台灣飼料工業部門的磷進口量的一半。 On the other hand, sewage sludge contains several percent of phosphorus, which is one of the main components of fertilizers. If the phosphorus content is estimated at 10% P2O5 , Taiwan has about 5,486 tons of phosphorus resources each year, which is equivalent to half of the annual phosphorus imports of Taiwan's feed industry.
目前液態肥料的製造方法主要有兩種。傳統之製造方法為利用各種有機質如：豆漿、牛奶、腐敗水果等，添加一些土壤有益微生物群，與水攪拌混合均勻，有氧堆肥放置2~3週後產出之滲出液，即為液態肥料。There are two main methods for making liquid fertilizer. The traditional method is to use various organic substances such as soy milk, milk, rotten fruit, etc., add some beneficial soil microorganisms, mix them with water, and aerobically compost them for 2 to 3 weeks. The exudate produced is liquid fertilizer.
另一種製造方法為利用尿素為主要之液體，額外添加磷酸一銨、硝酸鉀、硫酸鎂、納豆氨基酸、海草精、氫氧化鉀等，依不同比例之氮、磷、鉀等製作而成。傳統之製造方法所需時間較長，且可能發生堆肥臭味問題。Another manufacturing method is to use urea as the main liquid, and add additional monoammonium phosphate, potassium nitrate, magnesium sulfate, natto amino acid, seaweed extract, potassium hydroxide, etc. to make it according to different proportions of nitrogen, phosphorus, potassium, etc. Traditional manufacturing methods take a long time and may cause compost odor issues.
另一種製造方法需使用價格昂貴的尿素，且需添加額外的化學藥劑，成本較高。Another manufacturing method requires the use of expensive urea and the addition of additional chemicals, which is more expensive.
目前下水汙泥中的磷資源回收方式，大多利用強酸浸漬法、強鹼浸漬法、多次酸鹼浸漬法等方法，將下水汙泥中的磷和銅、鉛、鉻、鎘、錳、鎳、鋅等重金屬一起浸漬出，再使用選擇性吸附、沉澱法、離子交換法等方法，去除浸漬液中重金屬，最後使用氫氧化鈉或鹽酸調整pH值至8~9，再添加氯化鎂(MgCl 2·6H 2O)和氯化銨 (NH 4Cl)、氫氧化銨(NH 4OH)和氧化鎂(MgO)等方法，合成鳥糞石，以鳥糞石的型態回收磷資源。鳥糞石可取代磷礦石。上述方法雖可從下水汙泥中回收磷製成鳥糞石，惟亦存在著須使用大量強酸或強鹼，以及氯化鎂和氯化銨或氧化鎂和氫氧化銨等化學藥品，回收過程中亦產生二次污染廢水之問題。 At present, the phosphorus resource recovery methods in sewage sludge mostly use strong acid impregnation, strong alkali impregnation, multiple acid-alkali impregnation and other methods to remove phosphorus and copper, lead, chromium, cadmium, manganese, nickel, etc. in the sewage sludge. Heavy metals such as zinc are impregnated together, and then selective adsorption, precipitation, ion exchange and other methods are used to remove heavy metals in the impregnation solution. Finally, sodium hydroxide or hydrochloric acid is used to adjust the pH value to 8~9, and then magnesium chloride (MgCl 2 · 6H 2 O) and ammonium chloride (NH 4 Cl), ammonium hydroxide (NH 4 OH) and magnesium oxide (MgO) to synthesize struvite, and recover phosphorus resources in the form of struvite. Struvite can replace phosphate rock. Although the above method can recover phosphorus from sewage sludge to make struvite, it also requires the use of a large amount of strong acid or alkali, as well as chemicals such as magnesium chloride and ammonium chloride or magnesium oxide and ammonium hydroxide. The problem of secondary polluted wastewater.
是以，本案發明人在觀察上述議題後，而遂有本發明之產生。Therefore, the inventor of this case came up with the present invention after observing the above issues.
為達上述目的，本發明提供一種液態肥料製造方法，本方法可從下水汙泥製造液態肥料，將下水汙泥與鈣化合物混合後進行熱處理，熱處理後所得之下水汙泥使用混合有機酸進行浸漬處理，經固液分離後，於所得之浸漬液中添加鉀化合物及銨化合物後，製成液態肥料，製成之液態肥料可促進植物生長，且其中之重金屬含量低於我國液態肥料之重金屬含量標準，本方法可達成下水汙泥肥料化，減少磷資源浪費，進而減少下水汙泥的最終處理量。In order to achieve the above object, the present invention provides a method for manufacturing liquid fertilizer. This method can produce liquid fertilizer from sewage sludge. The sewage sludge is mixed with a calcium compound and then heat-treated. The heat-treated sewage sludge obtained is impregnated with a mixed organic acid. After solid-liquid separation, potassium compounds and ammonium compounds are added to the resulting impregnation solution to make liquid fertilizer. The liquid fertilizer can promote plant growth, and the heavy metal content in it is lower than the heavy metal content of liquid fertilizers in my country. According to the standard, this method can achieve fertilization of sewage sludge, reduce the waste of phosphorus resources, and thereby reduce the final disposal volume of sewage sludge.
添加鈣化合物與下水汙泥混合後，於相對低溫下進行熱處理，將下水汙泥中的各種型態的磷，轉換成較易溶解的磷灰石磷型態，再使用對環境衝擊較小的混合有機酸(檸檬酸及醋酸)進行浸漬，經固液分離後，再添加鉀化合物和銨化合物至浸漬液中，製成液態肥料。製成之液態肥料可促進植物生長，且其中之重金屬含量低於我國液態肥料之重金屬含量標準。After adding calcium compounds and mixing with sewage sludge, heat treatment is performed at a relatively low temperature to convert various forms of phosphorus in sewage sludge into a more soluble apatite phosphorus form. Then, mixed organic acids (citric acid and acetic acid) with less impact on the environment are used for impregnation. After solid-liquid separation, potassium compounds and ammonium compounds are added to the impregnation liquid to produce liquid fertilizer. The produced liquid fertilizer can promote plant growth, and the heavy metal content in it is lower than the heavy metal content standard of liquid fertilizer in Taiwan.
較佳地，將脫水乾燥後的下水汙泥，添加定量之鈣化合物，於一溫度及一時間下，於高溫爐中進行熱處理。Preferably, a certain amount of calcium compound is added to the dehydrated and dried sewage sludge, and heat treatment is performed in a high-temperature furnace at a certain temperature and for a certain time.
較佳地，混合有機酸浸漬的最佳條件為下水汙泥與8wt %之鈣化合物混合，於溫度300℃、時間2小時下進行熱處理後，以混合有機酸(檸檬酸和醋酸，濃度比1.042)，於常溫下，時間2小時，液固比10 ml/g，進行浸漬，得到磷之浸漬率約為85%，所有重金屬之浸漬率皆低於50%的結果。Preferably, the best condition for mixed organic acid impregnation is to mix sewage sludge with 8wt% calcium compounds, heat treatment at a temperature of 300°C for 2 hours, and then mix organic acids (citric acid and acetic acid, concentration ratio 1.042 ), impregnated at room temperature for 2 hours, with a liquid-to-solid ratio of 10 ml/g, and the impregnation rate of phosphorus was approximately 85%, and the impregnation rate of all heavy metals was less than 50%.
爲使熟悉該項技藝人士瞭解本發明之目的、特徵及功效，茲藉由下述具體實施例，並配合所附之圖式，對本發明詳加說明如下。In order to enable persons familiar with the art to understand the purpose, features and effects of the present invention, the present invention is described in detail as follows through the following specific embodiments and in conjunction with the attached drawings.
現在將參照其中示出本發明概念的示例性實施例的附圖在下文中更充分地闡述本發明概念。以下藉由參照附圖更詳細地闡述的示例性實施例，本發明概念的優點及特徵以及其達成方法將顯而易見。The inventive concept will now be described more fully below with reference to the accompanying drawings in which exemplary embodiments of the inventive concept are shown. Advantages and features of the inventive concept and methods of achieving the same will become apparent from the exemplary embodiments described in more detail below with reference to the accompanying drawings.
本文所用術語僅用於闡述特定實施例，而並非旨在限制本發明。除非上下文中清楚地另外指明，否則本文所用的單數形式的用語「一」及「該」旨在亦包括複數形式。本文所用的用語「及/或」包括相關所列項其中一或多者的任意及所有組合。應理解，當稱元件「連接」或「耦合」至另一元件時，所述元件可直接連接或耦合至所述另一元件或可存在中間元件。The terms used herein are used only to describe specific embodiments and are not intended to limit the present invention. Unless the context clearly indicates otherwise, the singular forms of the terms "a", "an" and "the" used herein are intended to include the plural forms as well. The term "and/or" used herein includes any and all combinations of one or more of the relevant listed items. It should be understood that when an element is said to be "connected" or "coupled" to another element, the element may be directly connected or coupled to the other element or there may be intermediate elements.
本文中參照圖來闡述示例性實施例，其中所述圖是理想化示例性說明圖。因此，預期存在由例如製造技術及/或容差所造成的相對於圖示形狀的偏離。因此，圖中所示的區為示意性的，且其形狀並非旨在說明裝置的區的實際形狀、亦並非旨在限制示例性實施例的範圍。Example embodiments are described herein with reference to the drawings, which are idealized illustrations of the examples. Therefore, deviations from the shapes illustrated are expected to occur due, for example, to manufacturing techniques and/or tolerances. Accordingly, the regions shown in the figures are schematic and their shapes are not intended to illustrate the actual shapes of the regions of the device nor to limit the scope of the exemplary embodiments.
本發明液態肥料製造方法請參閱圖1，圖1為根據本發明之液態肥料製造方法的流程圖。液態肥料製造方法主要包含步驟S100~S400，其中，步驟S100~S300為針對下水汙泥的處理，也可以說明為液態肥料製造的前處理，透過步驟S100~S300來獲得步驟S400所需的原料。 Please refer to Figure 1 for the liquid fertilizer manufacturing method of the present invention. Figure 1 is a flow chart of the liquid fertilizer manufacturing method according to the present invention. The liquid fertilizer manufacturing method mainly includes steps S100~S400, wherein steps S100~S300 are for the treatment of sewage sludge, which can also be described as the pre-treatment of liquid fertilizer manufacturing. The raw materials required for step S400 are obtained through steps S100~S300.
在步驟S100中，將脫水乾燥後的下水汙泥，添加定量之鈣化合物，於一第一溫度及一第一時間下，於高溫爐中進行熱處理。 In step S100, a certain amount of calcium compound is added to the dehydrated and dried sewage sludge, and heat-treated in a high-temperature furnace at a first temperature and for a first time.
在步驟S200中，使用一混合比例之有機酸為浸漬液，於常溫下，經過一浸漬時間，對熱處理後的下水汙泥進行浸漬，其中，有機酸為檸檬酸和醋酸的混合液。 In step S200, an organic acid with a mixing ratio is used as the impregnation liquid, and the heat-treated sewage sludge is impregnated at normal temperature for an impregnation time, wherein the organic acid is a mixture of citric acid and acetic acid.
在步驟S300中，加入混合有機酸的下水汙泥經過一第二時間的浸漬之後，將混合有機酸的下水汙泥進行固液分離。 In step S300, after the sewage sludge mixed with organic acids is added and soaked for a second period of time, solid-liquid separation is performed on the sewage sludge mixed with organic acids.
在步驟S400中，將固液分離後的浸漬液，進行液態肥料製作，依照浸漬液中的磷含量，於浸漬液體中添加鉀化合物做為鉀源和銨化合物做為氮源，來製成液態肥料。 In step S400, the soaking liquid after solid-liquid separation is used to make liquid fertilizer. According to the phosphorus content in the soaking liquid, potassium compounds as potassium sources and ammonium compounds as nitrogen sources are added to the soaking liquid to make liquid fertilizer.
具體地，本發明實施例的實驗材料及數據分析如圖2至圖8所示，為了尋找出最佳的溫度、時間、比例。 Specifically, the experimental materials and data analysis of the embodiment of the present invention are shown in Figures 2 to 8, in order to find the optimal temperature, time, and ratio.
首先，步驟S100，添加鈣化合物的量以及熱處理的時間、溫度，皆會影響後續的效果，熱處理時間即為第一時間，熱處理溫度即為第一溫度，因此，以下水汙泥1g，熱處理溫度200℃、熱處理時間2小時為固定因素，在下水汙泥中添加不同含量的鈣化合物進行熱處理，其數據如圖2所顯示。 First, in step S100, the amount of calcium compound added and the time and temperature of heat treatment will all affect the subsequent effects. The heat treatment time is the first time, and the heat treatment temperature is the first temperature. Therefore, the following water sludge 1g, heat treatment temperature 200°C and a heat treatment time of 2 hours are fixed factors. Different contents of calcium compounds are added to the sewage sludge for heat treatment. The data is shown in Figure 2.
由圖2中可以看見，當鈣化合物添加量為2wt.%時，下水汙泥中各種磷型態含量有所改變，非磷灰石磷含量減少至20-25%，磷灰石磷含量提升至35-39%，有機磷含量並未有變化。 It can be seen from Figure 2 that when the calcium compound addition amount is 2wt.%, the content of various phosphorus forms in the sewage sludge changes. The non-apatite phosphorus content is reduced to 20-25%, and the apatite phosphorus content is increased. to 35-39%, the organophosphorus content did not change.
隨著鈣化合物添加量的增加，非磷灰石磷含量並未減少，磷灰石磷含量隨之提升，而有機磷含量隨之減少。當鈣化合物添加量為8wt.%時，下水汙泥中非磷灰石磷含量並未減少，磷灰石磷含量提升至50%，有機磷含量減少至35-39%。故鈣化合物添加量範圍為7-15wt.%，以8wt.%為最佳鈣化合物添加量。 As the addition of calcium compounds increases, the non-apatite phosphorus content does not decrease, the apatite phosphorus content increases, and the organic phosphorus content decreases. When the calcium compound addition amount is 8wt.%, the non-apatite phosphorus content in the sewage sludge does not decrease, the apatite phosphorus content increases to 50%, and the organic phosphorus content decreases to 35-39%. Therefore, the range of calcium compound addition is 7-15wt.%, and 8wt.% is the optimal calcium compound addition.
接著，以下水汙泥1g，添加8wt.%鈣化合物、熱處理時間2小時為固定因素，於不同溫度下進行熱處理，而熱處理溫度對下水汙泥中各種磷型態含量之影響如圖3所示。 Next, 1g of sewage sludge was heat treated at different temperatures with 8wt.% calcium compound added and 2 hours of heat treatment time as fixed factors. The effect of heat treatment temperature on the content of various phosphorus forms in sewage sludge is shown in Figure 3.
由圖3中可以看見，於200℃時，下水汙泥中非磷灰石磷含量為18%、磷灰石磷含量為50%、有機磷含量為38%。隨著熱處理溫度的提高，非磷灰石磷含量有些微的減少、磷灰石磷含量隨之增加、有機磷含量隨之減少。於300℃時，下水汙泥中非磷灰石磷含量減少至9%、磷灰石磷含量增加至90%、有機磷含量減少至1%。故熱處理溫度即第一溫度範圍為250-450℃，以300℃為最佳熱處理溫度。 As can be seen from Figure 3, at 200°C, the non-apatite phosphorus content in sewage sludge is 18%, the apatite phosphorus content is 50%, and the organic phosphorus content is 38%. As the heat treatment temperature increases, the non-apatite phosphorus content slightly decreases, the apatite phosphorus content increases, and the organic phosphorus content decreases. At 300°C, the non-apatite phosphorus content in sewage sludge decreases to 9%, the apatite phosphorus content increases to 90%, and the organic phosphorus content decreases to 1%. Therefore, the heat treatment temperature, that is, the first temperature range is 250-450°C, and 300°C is the optimal heat treatment temperature.
接著，下水汙泥1g，添加8wt.%鈣化合物、熱處理溫度300℃為固定因素，於不同時間下進行熱處理，而熱處理時間對下水汙泥中各種磷型態含量之影響如圖4所示。 Next, 1g of sewage sludge was added with 8wt.% calcium compound, and the heat treatment temperature was 300°C as a fixed factor. Heat treatment was performed at different times. The effect of heat treatment time on the content of various phosphorus forms in the sewage sludge is shown in Figure 4.
在熱處理時間30分鐘時，非磷灰石磷含量為18%、磷灰石磷含量為40%、有機磷含量為46%。隨著熱處理時間增加，下水汙泥中各種磷型態含量也隨之變化。於熱處理時間2小時時，非磷灰石磷含量減少至8%、磷灰石磷含量增加至90%、有機磷含量減少至1%。故熱處理時間即第一時間範圍為2-4hr，以2hr為最佳熱處理時間。 When the heat treatment time is 30 minutes, the non-apatite phosphorus content is 18%, the apatite phosphorus content is 40%, and the organic phosphorus content is 46%. As the heat treatment time increases, the contents of various phosphorus forms in sewage sludge also change. When the heat treatment time was 2 hours, the non-apatite phosphorus content decreased to 8%, the apatite phosphorus content increased to 90%, and the organic phosphorus content decreased to 1%. Therefore, the heat treatment time, that is, the first time range is 2-4hr, and 2hr is the optimal heat treatment time.
在步驟S200中，熱處理後的下水汙泥混合有機酸浸漬，首先確定添加鈣化合物是否對下水汙泥混合有機酸浸漬有效，因此，以混合有機酸(檸檬酸和醋酸濃度比2.083)、常溫下浸漬時間6小時、浸漬液固比10ml/g，對有添加鈣化合物與無添加鈣化合物進行熱處理之下水汙泥進行浸漬後，浸漬殘渣中含有各種磷型態含量之比較，如圖5所示。 In step S200, the heat-treated sewage sludge is mixed with organic acid for leaching. First, it is determined whether the addition of calcium compounds is effective for the mixed organic acid leaching of sewage sludge. Therefore, the sewage sludge with and without calcium compounds added for heat treatment is leached with mixed organic acid (citric acid and acetic acid concentration ratio 2.083), leaching time 6 hours at room temperature, and leaching liquid-solid ratio 10ml/g. The contents of various phosphorus forms in the leaching residues are compared, as shown in Figure 5.
由圖5中可以看見，未添加鈣化合物進行熱處理之下水汙泥，浸漬殘渣中仍含有大量的有機磷和非磷灰石磷，使用混合有機酸無法將下水汙泥中之有機磷和非磷灰石磷浸出；而添加鈣化合物進行熱處理後之下水汙泥，有機磷完全轉換成磷灰石磷，因而提高混合有機酸之浸漬結果，浸漬殘渣中僅含有少量非磷灰石磷未被浸出。 As can be seen from Figure 5, the sewage sludge without adding calcium compounds for heat treatment still contains a large amount of organic phosphorus and non-apatite phosphorus in the leaching residue, and the organic phosphorus and non-apatite phosphorus in the sewage sludge cannot be leached out by using mixed organic acid; while the sewage sludge after adding calcium compounds for heat treatment, the organic phosphorus is completely converted into apatite phosphorus, thus improving the leaching result of mixed organic acid, and only a small amount of non-apatite phosphorus is contained in the leaching residue that is not leached out.
接著，以不同的有機酸濃度比(檸檬酸與醋酸濃度比)做為變因，於常溫下、浸漬時間6小時、液固比10ml/g，進行浸漬，有機酸(檸檬酸(CA)與醋酸(AA))濃度比對磷及重金屬浸漬率之影響，如圖6所示。 Next, different organic acid concentration ratios (citric acid to acetic acid concentration ratios) were used as variables, and the immersion was carried out at room temperature, immersion time of 6 hours, and liquid-solid ratio of 10ml/g. The effect of the organic acid (citric acid (CA) to acetic acid (AA)) concentration ratio on the immersion rate of phosphorus and heavy metals is shown in Figure 6.
由圖6中可以看見，當混合有機酸濃度比為0.208時，磷之浸漬率約為75%，重金屬浸漬率皆低於60%；隨著混合有機酸濃度比的增加，磷之浸漬率隨之增加，重金屬浸漬率也隨之增加；當混合有機酸濃度比為1.042時，磷之浸漬率提升至87%，重金屬浸漬率皆無明顯提升；而當混合有機酸濃度比為2.083時，磷之浸漬率維持不變，重金屬中鎳(Ni)和鉛(Pb)浸漬率皆有所增加。故混合有機酸中檸檬酸與醋酸的濃度比範圍為0.521-1.042，以1.042為最佳混合有機酸濃度比。 It can be seen from Figure 6 that when the mixed organic acid concentration ratio is 0.208, the phosphorus impregnation rate is about 75%, and the heavy metal impregnation rate is less than 60%. As the mixed organic acid concentration ratio increases, the phosphorus impregnation rate increases. As the concentration ratio of mixed organic acids increases, the impregnation rate of heavy metals also increases; when the mixed organic acid concentration ratio is 1.042, the phosphorus impregnation rate increases to 87%, and the heavy metal impregnation rate does not increase significantly; and when the mixed organic acid concentration ratio is 2.083, the phosphorus impregnation rate increases The impregnation rate remains unchanged, and the impregnation rates of nickel (Ni) and lead (Pb) among heavy metals have increased. Therefore, the concentration ratio of citric acid and acetic acid in the mixed organic acid ranges from 0.521 to 1.042, and 1.042 is the optimal mixed organic acid concentration ratio.
接著，以不同浸漬時間為變因，讓熱處理後之下水汙泥1g，在混合有機酸(檸檬酸與醋酸)濃度比1.042，於常溫下、液固比10ml/g條件下浸漬，實驗浸漬時間對磷及重金屬浸漬率之影響，如圖7所示。 Then, using different immersion times as variables, 1g of heat-treated sewage sludge was immersed in a mixed organic acid (citric acid and acetic acid) concentration ratio of 1.042 at room temperature and a liquid-to-solid ratio of 10ml/g. Experimental immersion time The influence on the impregnation rate of phosphorus and heavy metals is shown in Figure 7.
由圖7中可以看見，當浸漬時間為0.5小時時，磷之浸漬率約為65%，所有重金屬之浸漬率都低於40%，隨著浸漬時間的增加，磷之浸漬率和重金屬之浸漬率皆隨之增加，當浸漬時間為2小時時，磷之浸漬率增加至約為85%，所有重金屬之浸漬率都低於50%，而當浸漬時間超過2小時時，磷之浸漬率並未增加，重金屬中Ni和Zn浸漬率增加至55%，Cu、Pb、Cr浸漬率增加至35%。為了避免有更多的重金屬被浸漬出，故浸漬時間範圍為1-2hr，以2hr為最佳浸漬時間。 It can be seen from Figure 7 that when the impregnation time is 0.5 hours, the impregnation rate of phosphorus is about 65%, and the impregnation rate of all heavy metals is less than 40%. As the impregnation time increases, the impregnation rate of phosphorus and the impregnation rate of heavy metals The impregnation rates increase accordingly. When the impregnation time is 2 hours, the impregnation rate of phosphorus increases to about 85%, and the impregnation rates of all heavy metals are less than 50%. When the impregnation time exceeds 2 hours, the impregnation rate of phosphorus does not There is no increase, the impregnation rate of Ni and Zn in heavy metals increases to 55%, and the impregnation rate of Cu, Pb, and Cr increases to 35%. In order to avoid more heavy metals being impregnated, the impregnation time range is 1-2hr, with 2hr being the optimal impregnation time.
接著，以不同的浸漬液固比為變因，讓熱處理後之下水汙泥1g，在以混合有機酸(檸檬酸與醋酸)濃度比1.042，於常溫、浸漬時間2小時條件下，實驗漬液固比對磷及重金屬浸漬率之影響如圖8所示。 Next, with different immersion liquid-solid ratios as variables, 1g of heat-treated sewage sludge was immersed in a mixed organic acid (citric acid and acetic acid) with a concentration ratio of 1.042 at room temperature and an immersion time of 2 hours. The effect of the immersion liquid-solid ratio on the immersion rate of phosphorus and heavy metals is shown in Figure 8.
由圖8中可以看見，當液固比為5ml/g時，磷之浸漬率約為75%，所有重金屬之浸漬率皆低於50%，隨著液固比的增加，磷和重金屬的浸漬率也隨之增加，當液固比為10ml/g時，磷之浸漬率約提升至85%，所有重金屬之浸漬率皆低於50%，當液固比超過10ml/g時，磷之浸漬率並無變化，重金屬中之Ni和Zn浸漬率約增加至55%，Pb、Cu、Cr浸漬率約分別增加至45%、40、35%。故浸漬液固比範圍為6-15ml/g，以10ml/g為最佳浸漬液固比。 As can be seen from Figure 8, when the liquid-solid ratio is 5ml/g, the impregnation rate of phosphorus is about 75%, and the impregnation rates of all heavy metals are less than 50%. As the liquid-solid ratio increases, the impregnation rates of phosphorus and heavy metals also increase. When the liquid-solid ratio is 10ml/g, the impregnation rate of phosphorus is about 85%, and the impregnation rates of all heavy metals are less than 50%. When the liquid-solid ratio exceeds 10ml/g, the impregnation rate of phosphorus does not change. The impregnation rates of Ni and Zn among heavy metals increase to about 55%, and the impregnation rates of Pb, Cu, and Cr increase to about 45%, 40, and 35%, respectively. Therefore, the impregnation liquid-solid ratio range is 6-15ml/g, and 10ml/g is the best impregnation liquid-solid ratio.
具體地，綜合上述幾個實驗所整理出的結果，可以得到混合有機酸浸漬的最佳條件為下水汙泥與8wt%之鈣化合物混合，於溫度300℃、時間2小時下進行熱處理後，以混合有機酸(檸檬酸和醋酸，濃度比1.042)，於常溫下，浸漬時間2小時，液固比10ml/g，進行浸漬，得到磷之浸漬率約為85%，所有重金屬之浸漬率皆低於50%的結果。 Specifically, the results of the above experiments show that the best conditions for mixed organic acid leaching are to mix sewage sludge with 8wt% calcium compounds, heat treat at 300℃ for 2 hours, and then leaching with mixed organic acid (citric acid and acetic acid, concentration ratio 1.042) at room temperature for 2 hours, liquid-solid ratio 10ml/g, and obtain a phosphorus leaching rate of about 85%, and the leaching rates of all heavy metals are less than 50%.
步驟S300固液分離，可以應用離心、過濾、壓濾等進行方式。 Step S300 solid-liquid separation can be performed by centrifugation, filtration, pressure filtration, etc.
在步驟S400製作液態肥料，固液分離後所獲得之浸漬液，依浸漬液中的磷含量，以磷：氮：鉀之莫耳比1：1-2：1-3之比例，添加鉀化合物做為鉀源和銨化合物做為氮源，製成液態肥料。 In step S400, liquid fertilizer is produced. To the impregnation liquid obtained after solid-liquid separation, a potassium compound is added according to the phosphorus content in the impregnation liquid at a molar ratio of phosphorus:nitrogen:potassium of 1:1-2:1-3. As a potassium source and ammonium compound as a nitrogen source, it can be made into liquid fertilizer.
具體地，為確認由本發明所製成之液態肥料對植物生長有所幫助，利用水耕方式種植植物，觀察比較21天後有無添加製成之液態肥料之生長情形。植物的初始狀態為4片葉子，根的長短約為3-4公分，經觀察後發現，未添加液態肥料種植21天後，植物的葉子依舊保持在4片，且根只有些微的成長1公分左右；而添加液態肥料種植21天後，植物皆有顯著生長，葉子生長至6-7片，且根的長度也生長至8-9公分，確認了本發明所製成的液態肥料之效果。 Specifically, in order to confirm that the liquid fertilizer made by the present invention is helpful for plant growth, plants were planted using hydroponics, and the growth conditions of the liquid fertilizer made with or without the addition of the liquid fertilizer were observed and compared after 21 days. The initial state of the plant has 4 leaves, and the root length is about 3-4 cm. After observation, it was found that after 21 days of planting without adding liquid fertilizer, the plant's leaves still remained at 4, and the roots only grew slightly by 1 cm. About 21 days after planting with liquid fertilizer, the plants all showed significant growth, with leaves growing to 6-7, and root length also growing to 8-9 centimeters, confirming the effect of the liquid fertilizer made by the present invention.
最後，再將本發明的技術特徵及其可達成之技術功效彙整如下： Finally, the technical features of the present invention and its achievable technical effects are summarized as follows:
其一，藉由本發明之液態肥料製造方法，達成下水汙泥肥料化，減少磷資源浪費，進而減少下水汙泥的最終處理量。 First, through the liquid fertilizer manufacturing method of the present invention, the sewage sludge is fertilized, reducing the waste of phosphorus resources, thereby reducing the final treatment volume of the sewage sludge.
其二，藉由本發明之液態肥料製造方法，製成之液態肥料可促進植物生長，且其中之重金屬含量低於我國液態肥料之重金屬含量標準。 Secondly, the liquid fertilizer produced by the liquid fertilizer manufacturing method of the present invention can promote plant growth, and the heavy metal content therein is lower than the heavy metal content standard of liquid fertilizer in our country.
其三，本方法不使用強酸或強鹼，也不產生廢水，可降低對環境的衝擊影響，此外，相較於使用強酸或強鹼，使用混合有機酸進行浸漬可避免下水汙泥中之重金屬大量浸出，可抑制液態肥料中之重金屬含量。 Third, this method does not use strong acids or strong bases, nor does it produce wastewater, which can reduce the impact on the environment. In addition, compared with the use of strong acids or strong bases, the use of mixed organic acids for leaching can avoid the large-scale leaching of heavy metals in sewage sludge and can suppress the heavy metal content in liquid fertilizers.
以上係藉由特定的具體實施例說明本發明之實施方式，所屬技術領域具有通常知識者可由本說明書所揭示之內容輕易地瞭解本發明之其他優點及功效。 The above is a specific and concrete example to illustrate the implementation of the present invention. Those with ordinary knowledge in the relevant technical field can easily understand the other advantages and effects of the present invention from the content disclosed in this manual.
以上所述僅為本發明之較佳實施例，並非用以限定本發明之範圍；凡其它未脫離本發明所揭示之精神下所完成之等效改變或修飾，均應包含在下述之專利範圍內。 The above descriptions are only preferred embodiments of the present invention and are not intended to limit the scope of the present invention; all other equivalent changes or modifications made without departing from the spirit disclosed in the present invention shall be included in the following patent scope. within.
S100、S200、S300、S400:步驟S100, S200, S300, S400: Steps
圖1為根據本發明之液態肥料製造方法的流程圖； 圖2為根據本發明之液態肥料製造方法的實驗數據示意圖： 圖3為根據本發明之液態肥料製造方法的另一實驗數據示意圖； 圖4為根據本發明之液態肥料製造方法的另一實驗數據示意圖； 圖5為根據本發明之液態肥料製造方法的另一實驗數據示意圖； 圖6為根據本發明之液態肥料製造方法的另一實驗數據示意圖； 圖7為根據本發明之液態肥料製造方法的另一實驗數據示意圖；以及 圖8為根據本發明之液態肥料製造方法的另一實驗數據示意圖。 Figure 1 is a flow chart of the liquid fertilizer manufacturing method according to the present invention; Figure 2 is a schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention: Figure 3 is another schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention; Figure 4 is another schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention; Figure 5 is another schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention; Figure 6 is another schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention; Figure 7 is another schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention; and Figure 8 is another schematic diagram of experimental data of the liquid fertilizer manufacturing method according to the present invention.
S100、S200、S300、S400:步驟 S100, S200, S300, S400: steps
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| CN102320873A (en) * | 2011-08-17 | 2012-01-18 | 中国科学院广州能源研究所 | Method for preparing composite slow-release fertilizer by common utilization of biomass and sludge |
| CN102476961A (en) * | 2010-11-29 | 2012-05-30 | 韩国科学技术研究院 | Method and apparatus for producing organic fertilizer with sewage and sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102476961A (en) * | 2010-11-29 | 2012-05-30 | 韩国科学技术研究院 | Method and apparatus for producing organic fertilizer with sewage and sludge |
| CN102320873A (en) * | 2011-08-17 | 2012-01-18 | 中国科学院广州能源研究所 | Method for preparing composite slow-release fertilizer by common utilization of biomass and sludge |
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