CN115259962A - Preparation method of livestock and poultry manure biochar-based slow-release phosphorus and potassium fertilizer - Google Patents
Preparation method of livestock and poultry manure biochar-based slow-release phosphorus and potassium fertilizer Download PDFInfo
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- 239000010871 livestock manure Substances 0.000 title claims abstract description 64
- 210000003608 fece Anatomy 0.000 title claims abstract description 63
- 244000144972 livestock Species 0.000 title claims abstract description 40
- 244000144977 poultry Species 0.000 title claims abstract description 40
- 239000003337 fertilizer Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title abstract description 51
- 239000011591 potassium Substances 0.000 title abstract description 51
- 229910052700 potassium Inorganic materials 0.000 title abstract description 51
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 49
- 239000011574 phosphorus Substances 0.000 title abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 49
- 238000000197 pyrolysis Methods 0.000 claims abstract description 19
- 238000005469 granulation Methods 0.000 claims abstract description 14
- 230000003179 granulation Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RDXARWSSOJYNLI-UHFFFAOYSA-N [P].[K] Chemical compound [P].[K] RDXARWSSOJYNLI-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000011575 calcium Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 241000272525 Anas platyrhynchos Species 0.000 claims description 2
- 241000287828 Gallus gallus Species 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 102000020897 Formins Human genes 0.000 claims 1
- 108091022623 Formins Proteins 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000013270 controlled release Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000002686 phosphate fertilizer Substances 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 229960003975 potassium Drugs 0.000 description 45
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 229960005069 calcium Drugs 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229910017625 MgSiO Inorganic materials 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- -1 (PO 4 ) 3 OH Chemical class 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
Description
技术领域technical field
本发明涉及属于固体废弃物资源化利用技术领域，特别涉及一种畜禽粪便生物炭基缓释磷钾肥的制备方法。The invention relates to the technical field of resource utilization of solid waste, in particular to a preparation method of livestock and poultry manure biochar-based slow-release phosphorus and potassium fertilizer.
背景技术Background technique
随着集约化养殖业的快速发展，我国年产畜禽粪便约38亿吨，位居世界之首。在我国畜禽养殖中广泛应用，因动物无法完全吸收或代谢饲料中的抗生素，导致绝大部抗生分抗生素以原药形式富集到畜禽粪便中，携带大量抗生素的畜禽粪便施入土壤后，容易造成环境中出现耐药菌与抗性基因，给人类健康构成巨大威胁。另外，由于饲养管理不当、气候异常、疫病感染等因素，养殖场常出现携带大量病毒细菌的粪便，对居民生活和畜禽养殖业发展等产生了疾病卫生方面的隐患，威胁着动物食品和生态环境安全。堆肥和厌氧发酵可有效消减四环素类抗生素，对抗性基因的扩散和传播也具有一定的控制效果，却无法彻底降解和杀灭畜禽粪便中的抗生素与病原菌。因此，急需寻找新的技术方法实现畜禽粪便的无害化处理和应用。With the rapid development of intensive breeding industry, my country's annual output of livestock and poultry manure is about 3.8 billion tons, ranking first in the world. It is widely used in livestock and poultry breeding in my country. Because animals cannot completely absorb or metabolize antibiotics in feed, most antibiotics are enriched in the form of raw drugs in livestock and poultry manure, and livestock and poultry manure carrying a large amount of antibiotics is applied to the soil. Finally, it is easy to cause drug-resistant bacteria and resistance genes to appear in the environment, posing a huge threat to human health. In addition, due to factors such as improper feeding management, abnormal climate, and infection of epidemic diseases, feces often appear in farms carrying a large amount of virus and bacteria, which has caused hidden dangers in terms of disease and hygiene to the lives of residents and the development of livestock and poultry breeding, threatening animal food and ecology. environment safety. Composting and anaerobic fermentation can effectively reduce tetracycline antibiotics, and also have a certain control effect on the spread and spread of resistance genes, but they cannot completely degrade and kill antibiotics and pathogenic bacteria in livestock and poultry manure. Therefore, it is urgent to find new technical methods to realize the harmless treatment and application of livestock and poultry manure.
近年来，畜禽粪便的热解炭化技术得到了广泛关注。该技术将畜禽粪便通过绝氧中温炭化，彻底分解病原菌和抗生素，不仅能够钝化有害重金属，而且还能够将粪便中绝大部分磷、钾元素保留在生物炭中，并获得富含磷、钾的生物炭，成为一种潜在肥料。磷、钾对地球上所有生命的重要性是毋庸置疑的，作为三大营养素，它是现代矿物肥料的重要组成部分；也是动植物生命活动不可或缺的营养元素。然而，由于畜禽粪便中磷含量较钾高，其比例不符合大多数作物需求。另外，畜禽粪便生物炭中磷主要以钙磷形态存在，其有效性很低，作物难利用，而钾有效性很高，易流失。因此，开发改善畜禽粪便生物炭中磷钾肥效的技术方案，对于畜禽粪污的资源化、土壤改良和作物生长等方面都具有重要意义。In recent years, the pyrolysis carbonization technology of livestock and poultry manure has received extensive attention. This technology uses anaerobic medium-temperature carbonization of livestock and poultry manure to completely decompose pathogenic bacteria and antibiotics. It can not only passivate harmful heavy metals, but also retain most of the phosphorus and potassium elements in the manure in biochar, and obtain phosphorus-rich, Potassium biochar, becoming a potential fertilizer. The importance of phosphorus and potassium to all life on earth is unquestionable. As the three major nutrients, it is an important part of modern mineral fertilizers; it is also an indispensable nutrient element for animal and plant life activities. However, due to the higher content of phosphorus than potassium in livestock and poultry manure, its ratio does not meet the requirements of most crops. In addition, phosphorus in livestock and poultry manure biochar mainly exists in the form of calcium and phosphorus, which has low availability and is difficult to use by crops, while potassium has high availability and is easy to lose. Therefore, the development of technical solutions to improve the efficiency of phosphorus and potassium fertilizers in livestock and poultry manure biochar is of great significance for the resource utilization of livestock and poultry manure, soil improvement and crop growth.
发明内容Contents of the invention
发明目的：针对现有技术中存在的问题，本发明提供一种畜禽粪便生物炭基缓释磷钾肥的制备方法，该方法成本低廉、肥效高、养分比例可控的生物炭基缓释肥。Purpose of the invention: Aiming at the problems existing in the prior art, the present invention provides a preparation method of livestock and poultry manure biochar-based slow-release phosphorus and potassium fertilizer, which is a biochar-based slow-release fertilizer with low cost, high fertilizer efficiency and controllable nutrient ratio .
技术方案：本发明提供了一种畜禽粪便生物炭基缓释磷钾肥的制备方法，该方法包括以下步骤：Technical solution: The invention provides a method for preparing livestock and poultry manure biochar-based slow-release phosphorus and potassium fertilizer, which comprises the following steps:
(1)混合：将畜禽粪便与钾盐、钙盐按照K/Ca/P比例为3∶4∶3-6∶3∶3的比例混合，并充分搅拌20-30min，得到混合物；(1) Mixing: mixing livestock and poultry manure with potassium salt and calcium salt according to the K/Ca/P ratio of 3:4:3-6:3:3, and fully stirring for 20-30min to obtain the mixture;
(2)干燥：将混合物在90-105℃下空气干燥至含水量3-5％，得到干燥样品；(2) Drying: air-dry the mixture at 90-105°C to a water content of 3-5%, to obtain a dry sample;
(3)造粒：将干燥样品进行挤压造粒，得到颗粒大小范围为2-5mm的颗粒样品；(3) Granulation: Extrude and granulate the dried sample to obtain a granule sample with a particle size range of 2-5mm;
(4)热解：将颗粒样品以10～20℃min-1的速率升温至600～700℃进行限氧热解60-90min，冷却后获得畜禽粪便生物炭基缓释磷钾肥。(4) Pyrolysis: the granular sample is heated at a rate of 10-20°C min -1 to 600-700°C for 60-90 minutes of limited oxygen pyrolysis, and after cooling, the biochar-based slow-release phosphorus and potassium fertilizer of livestock and poultry manure is obtained.
优选地，步骤(1)中，所述畜禽粪便为以下任意一种或其组合：猪粪、牛粪、羊粪、鸡粪、鸭粪。Preferably, in step (1), the livestock and poultry manure is any one or combination of the following: pig manure, cow manure, sheep manure, chicken manure, duck manure.
优选地，步骤(1)中，所述钾盐为以下任意一种或其组合：草酸钾、乙酸钾、柠檬酸钾。Preferably, in step (1), the potassium salt is any one or combination of the following: potassium oxalate, potassium acetate, potassium citrate.
优选地，步骤(1)中，所述钙盐为以下任意一种或其组合：碳酸氢钙、磷酸二氢钙、硝酸钙。Preferably, in step (1), the calcium salt is any one or combination of the following: calcium bicarbonate, calcium dihydrogen phosphate, calcium nitrate.
优选地，步骤(3)中，所述挤压造粒为对辊式挤压造粒。Preferably, in step (3), the extrusion granulation is pair-roll extrusion granulation.
有益效果：本发明与现有技术相比较，具有如下显而易见的突出实质特点和显著优点：Beneficial effects: compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:
(1)本发明利用可溶性钾、钙盐调节畜禽粪便中K/Ca/P比例，使其在高温热解条件下形成KaCab(PO4)3OH(a+b/2＝9，a/(a+b)＜0.1)和KCaPO4，该化合物较羟基磷灰石溶解性高，能为作物提供有效磷；同时偏碱性钾盐添加可以提高生物炭的pH，进而为K2MgSiO4形成创造条件，该化合物较添加钾盐溶解度低，能为作物提供缓效钾。(1) The present invention utilizes soluble potassium and calcium salts to adjust the ratio of K/Ca/P in livestock and poultry manure to form K a Ca b (PO 4 ) 3 OH (a+b/2=9 , a/(a+b)<0.1) and KCaPO 4 , this compound is more soluble than hydroxyapatite, and can provide available phosphorus for crops; at the same time, the addition of alkaline potassium salt can increase the pH of biochar, thereby providing K 2 MgSiO 4 forms to create conditions, the compound has a lower solubility than the added potassium salt, and can provide slow-acting potassium for crops.
(2)本发明在热解处理前采用辊式挤压造粒工艺进行造粒，该操作简便，便于实现生产自动化控制，提高生产效率。另外，利用可溶性钾催化热解畜禽粪便过程中产生团聚效应，可进一步提升产品颗粒硬度，有利于产品包装和运输。(2) The present invention adopts roller extrusion granulation process to granulate before pyrolysis treatment, which is easy to operate, easy to realize automatic production control and improve production efficiency. In addition, the use of soluble potassium to catalyze the agglomeration effect in the process of pyrolyzing livestock and poultry manure can further increase the hardness of product particles, which is beneficial to product packaging and transportation.
(3)本发明将畜禽粪便原料含水量调整到3-5％之间，不但可以减少能源消耗，而且可提供合适的气化氛围，促进各化合物间的反应，进而有利于KaCab(PO4)3OH、KCaPO4和K2MgSiO4等化合物的形成。(3) The present invention adjusts the water content of livestock and poultry feces raw materials to between 3-5%, which not only reduces energy consumption, but also provides a suitable gasification atmosphere to promote the reaction between the compounds, which is beneficial to K a Ca b Formation of compounds such as (PO 4 ) 3 OH, KCaPO 4 and K 2 MgSiO 4 .
(4)本发明操作简单，成本较低，通过该方法制备的畜禽粪便生物炭基控释磷钾肥可有效解决现有畜禽粪便生物炭有效磷含量低而有效钾含量高的问题，使得畜禽粪便生物炭中的磷钾同时达到缓释效果，一次施用满足作物整个生长期对磷钾的需求，提高磷钾利用效率，减少化肥投入量。(4) The present invention is simple to operate, and cost is lower, and the livestock and poultry manure biochar-based controlled-release phosphorus and potassium fertilizer prepared by the method can effectively solve the problem that the available phosphorus content of the existing livestock and poultry manure biochar is low and the effective potassium content is high, making Phosphorus and potassium in livestock and poultry manure biochar can achieve a slow release effect at the same time, and one application can meet the demand for phosphorus and potassium throughout the growth period of crops, improve the utilization efficiency of phosphorus and potassium, and reduce the input of chemical fertilizers.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细的介绍。The present invention will be described in detail below in conjunction with specific embodiments.
实施方式1：Implementation mode 1:
为了说明钾盐添加、钙盐添加的作用，在本发明方法的基础上设置对照处理(对照组分别为无添加碳酸钾和氢氧化钙的对照组、仅添加碳酸钾、仅添加氢氧化钙)，具体步骤如下：In order to illustrate the effect of potassium salt addition and calcium salt addition, contrast treatment is set on the basis of the inventive method (control group is respectively the control group without adding salt of wormwood and calcium hydroxide, only adding salt of wormwood, only adding calcium hydroxide) ,Specific steps are as follows:
(1)混合：将猪粪与碳酸钾盐、氢氧化钙盐按照K/Ca/P比例为3∶4∶3进行混合，并采用机械式充分搅拌30min，得到混合物；(1) Mixing: mix pig manure with potassium carbonate salt and calcium hydroxide salt according to the K/Ca/P ratio of 3:4:3, and fully stir it mechanically for 30 minutes to obtain the mixture;
(2)干燥：将混合物在105℃下烘干至含水量3-5％，得到干燥样品；(2) Drying: drying the mixture at 105°C to a water content of 3-5% to obtain a dried sample;
(3)造粒：将干燥样品进行对辊式挤压造粒，颗粒大小范围为2-5mm；(3) Granulation: the dry sample is subjected to roller extrusion granulation, and the particle size range is 2-5mm;
(4)热解：将造粒样品以10℃min-1的速率升温至600℃进行限氧热解60min，冷却后获得畜禽粪便生物炭基缓释磷钾肥。(4) Pyrolysis: The granulated sample was heated to 600°C at a rate of 10°C min -1 for 60 minutes of oxygen-limited pyrolysis, and after cooling, the biochar-based slow-release phosphorus and potassium fertilizer of livestock and poultry manure was obtained.
猪粪生物炭中有效磷、速效磷和缓效钾分别采用HJ 704-2014土壤有效磷的测定、碳酸氢钠浸提-钼锑抗分光光度法和NY T 889-2004土壤速效钾和缓效钾含量的测定。Available phosphorus, available phosphorus and slow-acting potassium in pig manure biochar were determined by HJ 704-2014 soil available phosphorus, sodium bicarbonate extraction-molybdenum antimony anti-spectrophotometry and NY T 889-2004 soil available potassium and slow-acting potassium content determination.
表1钾、钙盐添加猪粪生物炭中有效钾、磷的含量Table 1 Contents of available potassium and phosphorus in pig manure biochar added with potassium and calcium salts
从表1可知，无添加猪粪生物炭中有效磷含量很低，而速效钾含量很高，不适合作为缓释肥料。与对照相比，碳酸钾的添加明显提高猪粪生物炭中有效磷的含量，氢氧化钙的添加明显增加缓释钾的含量，而同时添加碳酸钾和氢氧化钙能达到两种效果。It can be seen from Table 1 that the content of available phosphorus in biochar without adding pig manure is very low, but the content of available potassium is very high, which is not suitable as a slow-release fertilizer. Compared with the control, the addition of potassium carbonate significantly increased the content of available phosphorus in pig manure biochar, and the addition of calcium hydroxide significantly increased the content of slow-release potassium, while adding potassium carbonate and calcium hydroxide at the same time can achieve two effects.
实施方式2：Implementation mode 2:
为了说明调节K/Ca/P比例的作用，在本发明方法的基础上设置多种K/Ca/P比例处理和对照组(无添加碳酸钾和氢氧化钙)，具体步骤如下：In order to illustrate the effect of regulating the K/Ca/P ratio, multiple K/Ca/P ratios are set on the basis of the inventive method to process and a matched group (without adding salt of wormwood and calcium hydroxide), and the concrete steps are as follows:
(1)混合：将猪粪与碳酸钾盐、氢氧化钙盐按照K/Ca/P比例为2∶4∶3，3∶4∶3，6∶4∶3和8∶4∶3，进行混合，并采用机械式充分搅拌30min，得到混合物；(1) Mixing: pig manure, potassium carbonate and calcium hydroxide are mixed according to the K/Ca/P ratio of 2:4:3, 3:4:3, 6:4:3 and 8:4:3. Mix and fully stir for 30 minutes by mechanical means to obtain the mixture;
(2)干燥：将混合物在105℃下烘干至含水量3-5％，得到干燥样品；(2) Drying: drying the mixture at 105°C to a water content of 3-5% to obtain a dried sample;
(3)造粒：将干燥样品进行对辊式挤压造粒，颗粒大小范围为2-5mm；(3) Granulation: the dry sample is subjected to roller extrusion granulation, and the particle size range is 2-5mm;
(4)热解：将造粒样品以10℃min-1的速率升温至600℃进行限氧热解60min，冷却后获得畜禽粪便生物炭基缓释磷钾肥。(4) Pyrolysis: The granulated sample was heated to 600°C at a rate of 10°C min -1 for 60 minutes of oxygen-limited pyrolysis, and after cooling, the biochar-based slow-release phosphorus and potassium fertilizer of livestock and poultry manure was obtained.
猪粪生物炭中有效磷、速效磷和缓效钾分别采用HJ 704-2014土壤有效磷的测定、碳酸氢钠浸提-钼锑抗分光光度法和NY T 889-2004土壤速效钾和缓效钾含量的测定。Available phosphorus, available phosphorus and slow-acting potassium in pig manure biochar were determined by HJ 704-2014 soil available phosphorus, sodium bicarbonate extraction-molybdenum antimony anti-spectrophotometry and NY T 889-2004 soil available potassium and slow-acting potassium content determination.
表2钾钙磷比例调节对猪粪生物炭中有效钾磷的影响Table 2 The effect of adjusting the ratio of potassium, calcium and phosphorus on the available potassium and phosphorus in pig manure biochar
从表2可知，尽管调整钾钙磷比例为2∶4∶3条件下，猪粪生物炭中有效磷含量有所提升，但是其占全磷比例仍然很低。当调整钾钙磷比例为8∶4∶3时，速效钾含量及比例较高，但是缓效钾含量已经开始大幅降低。因此，调整钾钙磷比例在3∶4∶3-6∶4∶3之间为畜禽粪便生物炭基缓释磷钾肥的最佳条件。It can be seen from Table 2 that although the ratio of potassium, calcium and phosphorus is adjusted to 2:4:3, the content of available phosphorus in pig manure biochar has increased, but its proportion to total phosphorus is still very low. When the ratio of potassium, calcium and phosphorus is adjusted to 8:4:3, the content and ratio of quick-acting potassium are higher, but the content of slow-acting potassium has begun to decrease significantly. Therefore, adjusting the ratio of potassium, calcium and phosphorus between 3:4:3-6:4:3 is the best condition for livestock and poultry manure biochar-based slow-release phosphorus and potassium fertilizers.
实施方式3：Implementation mode 3:
为了说明热解温度的作用，在本发明方法的基础上设置多种热解温度处理，具体步骤如下：In order to illustrate the effect of pyrolysis temperature, multiple pyrolysis temperature treatments are set on the basis of the inventive method, and the concrete steps are as follows:
(1)混合：将猪粪与碳酸钾盐、氢氧化钙盐按照K/Ca/P比例为6∶4∶3，进行混合，并采用机械式充分搅拌30min，得到混合物；(1) Mixing: mix pig manure with potassium carbonate salt and calcium hydroxide salt according to the K/Ca/P ratio of 6:4:3, and fully stir it mechanically for 30 minutes to obtain the mixture;
(2)干燥：将混合物在90-105℃下烘干至含水量3-5％，得到干燥样品；(2) Drying: drying the mixture at 90-105°C to a water content of 3-5% to obtain a dry sample;
(3)造粒：将干燥样品进行对辊式挤压造粒，颗粒大小范围为2-5mm；(3) Granulation: the dry sample is subjected to roller extrusion granulation, and the particle size range is 2-5mm;
(4)热解：将造粒样品以10℃min-1的速率升温至300℃、400℃、500℃、600℃、700℃进行限氧热解60min，冷却后获得畜禽粪便生物炭基缓释磷钾肥。(4) Pyrolysis: Heat the granulated sample to 300°C, 400°C, 500°C, 600°C, 700°C at a rate of 10°C min -1 for 60 minutes of oxygen-limited pyrolysis, and obtain livestock and poultry feces biochar base after cooling Slow-release phosphorus and potassium fertilizers.
猪粪生物炭中有效磷、速效磷和缓效钾分别采用HJ 704-2014土壤有效磷的测定、碳酸氢钠浸提-钼锑抗分光光度法和NY T 889-2004土壤速效钾和缓效钾含量的测定。Available phosphorus, available phosphorus and slow-acting potassium in pig manure biochar were determined by HJ 704-2014 soil available phosphorus, sodium bicarbonate extraction-molybdenum antimony anti-spectrophotometry and NY T 889-2004 soil available potassium and slow-acting potassium content determination.
表3不同热解温度对猪粪生物炭中有效磷钾含量的影响Table 3 Effects of different pyrolysis temperatures on the content of available phosphorus and potassium in pig manure biochar
从表3可知，随着热解温度的升高，有效磷含量逐渐升高，达到600℃以上趋于稳定。速效磷含量随热解温度升高逐渐降低，而缓效钾的变化趋势相反。因此，本发明选择600-700℃为制备猪粪生物炭基缓释磷钾肥的热解温度。It can be seen from Table 3 that with the increase of pyrolysis temperature, the content of available phosphorus gradually increases and tends to be stable above 600 °C. The content of available phosphorus decreased gradually with the increase of pyrolysis temperature, while the change trend of slow-acting potassium was opposite. Therefore, the present invention selects 600-700° C. as the pyrolysis temperature for preparing pig manure biochar-based slow-release phosphorus and potassium fertilizers.
上述实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only for illustrating the technical concept and characteristics of the present invention, and its purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the scope of protection of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.
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