CN115259916A - Carbon-nitrogen combined fixing agent, preparation method thereof and application thereof in preparation of organic fertilizer - Google Patents
Carbon-nitrogen combined fixing agent, preparation method thereof and application thereof in preparation of organic fertilizer Download PDFInfo
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- CN115259916A CN115259916A CN202211113646.1A CN202211113646A CN115259916A CN 115259916 A CN115259916 A CN 115259916A CN 202211113646 A CN202211113646 A CN 202211113646A CN 115259916 A CN115259916 A CN 115259916A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003895 organic fertilizer Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229960000892 attapulgite Drugs 0.000 claims abstract description 66
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 8
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- 239000002028 Biomass Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003337 fertilizer Substances 0.000 claims description 3
- 239000000834 fixative Substances 0.000 claims 1
- 238000000855 fermentation Methods 0.000 abstract description 27
- 230000004151 fermentation Effects 0.000 abstract description 27
- 239000011148 porous material Substances 0.000 abstract description 11
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 abstract description 4
- 239000004927 clay Substances 0.000 description 24
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- -1 ammonia ions Chemical class 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 239000010871 livestock manure Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/10—Addition or removal of substances other than water or air to or from the material during the treatment
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method of a carbon-nitrogen combined fixing agent, which comprises the following steps: (1) Mixing attapulgite and phosphoric acid for reaction until no bubbles are generated basically, and controlling the pH value at the end point of the reaction to be 1 to 3; (2) And after the reaction is finished, directly drying the attapulgite without washing to obtain the carbon-nitrogen combined fixing agent. Compared with the prior art, the carbon-nitrogen combined fixing agent prepared by the method not only keeps the good adsorbability of the attapulgite, but also forms countless micro-reactors by utilizing the nano-pores in the attapulgite to quickly convert adsorbed ammonia nitrogen into slightly soluble ammonium salt, thoroughly solves the problem that the existing attapulgite-based nitrogen fixing agent has poor stability and is easy to desorb, and is an excellent fixing agent for reducing the loss of organic carbon and nitrogen in organic fertilizer fermentation.
Description
Technical Field
The invention belongs to the field of organic fertilizers, and particularly relates to a carbon-nitrogen combined fixing agent for reducing organic carbon and nitrogen loss in the fermentation process of an organic fertilizer and a preparation method thereof.
Background
Agricultural organic wastes such as livestock manure, crop straws and the like are rich in a large amount of nutrient elements such as nitrogen, phosphorus, potassium and the like and medium and trace nutrient elements such as calcium, copper, iron, zinc, manganese and the like, and have higher fertilizerThe material utilization value. The aerobic composting technology can effectively kill pathogenic bacteria, realize the stabilization of organic wastes, is beneficial to the cyclic utilization of nitrogen, phosphorus and potassium nutrient elements, and becomes one of the current effective ways for harmless and resource utilization of organic wastes. However, the problem of loss of organic carbon and nitrogen is generally existed in the process of decomposing organic matters by composting. The nitrogen in the compost body in the composting process mainly exists in the forms of ammonium nitrogen, nitrate nitrogen, organic nitrogen and ammonia gas. The nitrogen loss way in the composting process mainly comprises the following 3 aspects, namely, organic matters are decomposed and accumulated to enable ammonia nitrogen generated by the temperature rise of a compost body to volatilize; secondly, water-soluble nitrogen is lost along with the discharge of leachate, thirdly, a local anoxic environment is formed in the reactor body due to insufficient ventilation, and nitric oxide volatilization is caused due to denitrification reaction of nitrate nitrogen. Wherein the nitrogen loss of more than 46.8 percent to 77.4 percent is caused by the volatilization of ammonia gas. The loss of organic carbon is mainly mineralization of organic matter and conversion into CO 2 The carbon and nitrogen loss not only pollutes the environment, but also reduces the soil utilization value of the compost product, and limits the development and application of the composting technology. Therefore, how to reduce the loss of organic carbon and nitrogen in the compost has important significance for controlling resource waste and environmental pollution.
The attapulgite is a natural one-dimensional nano-scale water-containing magnesium-aluminum-rich silicate clay mineral, and the basic structural unit is formed by connecting a silicon-oxygen tetrahedral layer in indirect inverted arrangement and an octahedral layer in discontinuous arrangement. Wherein an octahedral layer is sandwiched between two continuous tetrahedral layers to form a 2: 1 type 'sandwich' layer chain structure. Natural attapulgite clay is often accompanied by opals, quartz, carbonates, etc., and at the same time, due to van der waals forces and hydrogen bonding, attapulgite clay rod crystals are generally present in the form of aggregates, limiting the properties and application range of the attapulgite clay. Therefore, it is generally necessary to remove impurities and dissociate the rod crystal aggregates by an appropriate method before use. The attapulgite clay can be partially depolymerized by acid activation treatment, so as to increase the specific surface area of the attapulgite clay, remove mineral impurities such as carbonate, etc., and the attapulgite is generally washed by water after the acid activation treatment, so as to remove unreacted acid and other impurity products.
The Chinese invention patent (201310447583.8) is a feed fermentation method using modified attapulgite clay as a nitrogen fixing agent, which takes high-temperature ammoniated straws as a feed fermentation substrate, takes the modified attapulgite clay as the nitrogen fixing agent, adopts mixed zymophyte to ferment the high-temperature ammoniated straws at high temperature, and the preparation of the modified attapulgite clay is as follows: crushing attapulgite clay, sieving with a 100-mesh sieve, adding the crushed attapulgite clay into a sulfuric acid solution with the concentration of 2mol/L, wherein the volume ratio of the attapulgite clay to the sulfuric acid solution is 1:10, stirring for 3 hours at room temperature, washing with distilled water until the pH value is 6, centrifuging, and drying the solid phase at 60 ℃ to obtain the modified attapulgite clay. The modified attapulgite still has the same effect as the conventional acid activation treatment, the adsorption capacity of the modified attapulgite is improved by increasing the specific surface area of the attapulgite, but the problem that the nitrogen fixation amount is limited by the specific surface area and the pore channel structure, the adsorption stability is poor and desorption is easy to occur due to the simple increase of the specific surface area.
Disclosure of Invention
In order to overcome the defects of the prior art, the inventor provides a preparation method of a carbon and nitrogen combined fixing agent on the basis of deeply understanding the structure and the characteristics of attapulgite and the cause of carbon and nitrogen loss in the organic fertilizer fermentation process.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a carbon-nitrogen combined fixing agent comprises the following steps:
(1) Mixing attapulgite and phosphoric acid for reaction until no bubbles are generated basically, and controlling the pH value at the end point of the reaction within 1-3;
(2) And after the reaction is finished, directly drying the attapulgite without washing to obtain the carbon-nitrogen combined fixing agent.
Preferably, the phosphoric acid is a phosphoric acid aqueous solution with the concentration of 10 to 15wt%, and the adding amount of the phosphoric acid is controlled to ensure that the attapulgite is completely wetted, so that the drying energy consumption can be saved.
More preferably, the mass ratio of the attapulgite to the phosphoric acid aqueous solution is 1.
The heating is beneficial to accelerating the escape of carbon dioxide gas and shortening the reaction time, and the reaction temperature is preferably 60 to 80 ℃.
Preferably, the drying is carried out until the water content of the carbon-nitrogen combined fixing agent is below 20 wt%.
More preferably, the water content of the carbon-nitrogen combined fixing agent is 15 to 18 wt%.
A carbon-nitrogen combined fixing agent prepared by the method.
The carbon and nitrogen combined fixing agent is applied to the preparation of organic fertilizer.
Preferably, the biomass raw material and the carbon and nitrogen combined fixing agent of claim 7 are mixed and fermented to obtain the organic fertilizer.
More preferably, the dosage of the carbon and nitrogen combined fixing agent is 5 to 10 percent of the dry weight of the biomass raw material.
The technical principle of the invention is as follows:
(1) Slightly soluble ammonium salt fixation principle
The conversion reaction of ammonium nitrogen and ammonia gas is a reversible reaction, the acidic condition is favorable for inhibiting the volatilization of the ammonia gas, but the ammonia gas can be released again when the pH value is increased.
After the attapulgite reacts with the phosphoric acid, magnesium in the attapulgite is dissolved and replaced by the phosphoric acid, the magnesium is converted into hydrogen phosphate, after the reaction, the attapulgite rod crystal aggregates are dissociated, the interlayer distance is enlarged, and the adsorption capacity is obviously enhanced. The aim of washing the attapulgite without water is to ensure that excessive phosphoric acid which is not completely reacted is kept in the attapulgite pores as much as possible and the generated phosphate (hydrogen) salt is kept in the attapulgite pores, which is the key point for realizing nitrogen fixation.
In the fermentation process of the organic fertilizer, ammonia nitrogen is adsorbed in the pores of the attapulgite, phosphoric acid in the pores provides an acidic microenvironment for promoting ammonia gas to be converted into ammonia ions, and the ammonia ions further react with phosphate (hydrogen) to generate slightly soluble ammonium salt, so that the ammonia nitrogen is completely fixed. The reaction is as follows:
NH 3 ↑+ H + ⇋ NH 4 +
Mg 5 Si 8 O 2 (OH 2 )(OH 2 ) 4 ·4H 2 O + 5H 3 PO 4 → H 10 Si 8 O 2 (OH 2 )(OH 2 ) 4 ·4H 2 O + 5Mg 2+ + 5PO 4 3- + 5H +
Mg 2+ + PO 4 3- + NH 4 + → NH 4 MgPO 4 ↓
(2) Principle of fixing carbon with nano-pore structure
In the organic fertilizer fermentation process, organic molecules are degraded, organic small molecules are directly adsorbed to attapulgite to enter the pore channels, the decomposition probability by microorganisms is reduced, mineralization is reduced, and the organic carbon nanometer pore channel fixation is realized.
(3) Organic-inorganic composite carbon fixation principle
Attapulgite natural nano materials are added in the fermentation process of the organic fertilizer, organic matters and the attapulgite are subjected to high-temperature composting to generate organic-inorganic complexes, and organic-inorganic composite fixation of organic carbon is realized.
Has the beneficial effects that:
1. compared with the direct mixing of the biomass raw material and the acid, the nano-pore of the attapulgite is equivalent to a plurality of micro-reactors, and the carbon and nitrogen combined fixing agent provided by the invention binds the phosphoric acid in the nano-pore of the attapulgite, so that the micro-reactors can obtain acid concentration far higher than that of the biomass raw material and the same amount of acid which can be directly mixed, the use amount of the acid can be reduced, and the influence of the acid liquid on the microbial fermentation can be avoided.
2. The carbon-nitrogen combined fixing agent not only keeps the good adsorbability of the attapulgite, but also utilizes countless micro-reactors formed by the nano-channels in the fixing agent to quickly convert the adsorbed ammonia nitrogen into slightly soluble ammonium salt, thereby thoroughly solving the problem that the attapulgite-based nitrogen fixing agent in the prior art has poor nitrogen fixation stability and is easy to desorb.
Drawings
FIG. 1 shows the effect of carbon and nitrogen combined fixing agent on the fermentation temperature of organic fertilizer.
FIG. 2 shows the influence of carbon and nitrogen combined fixing agent on the carbon and nitrogen emission reduction effect of organic fertilizer fermentation.
FIG. 3 is a comparison of carbon and nitrogen combined fixing agent and sulfuric acid modified attapulgite on carbon and nitrogen emission reduction effect of organic fertilizer fermentation.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples.
Example 1
Preparing a carbon-nitrogen combined fixing agent:
(1) Grinding attapulgite (purity is more than or equal to 80%) in a ball mill, and sieving with 400 mesh sieve.
(2) The 85wt% concentrated phosphoric acid is diluted by adding water to form dilute phosphoric acid with the concentration of 10wt% to 15 wt%.
(3) Slowly adding diluted phosphoric acid into the attapulgite powder under stirring of an anticorrosive stainless steel rotary drum, heating for 50min-60min at the temperature of 60-80 ℃ until the mixture does not generate bubbles and the final pH value of the mixture is 1-3, and stopping adding the diluted phosphoric acid (so that the attapulgite is completely wetted but does not generate obvious liquid, wherein the mass ratio of the attapulgite powder to the diluted phosphoric acid is about 1.30-1.
(4) And (4) continuously heating the mixture obtained in the step (3) at the temperature of 60-80 ℃ to evaporate water until the water content is reduced to 15-20%, thus obtaining the carbon-nitrogen combined fixing agent for organic fertilizer fermentation.
Example 2
(1) Removing gravels in the waste biomass such as livestock and poultry manure, crushing the gravels into particles with the diameter of 1-2cm, and adding the carbon-nitrogen combined fixing agent of the embodiment 1, wherein the weight of the carbon-nitrogen combined fixing agent is 5-10% of the dry weight of the waste biomass.
(2) Adding water to adjust the water content of the fermented material to 50% -55%, stacking the fermented material into long strips, wherein the bottom width is 2-3 m and the height is 1-1.5 m, and starting fermentation.
(3) And continuously monitoring the temperature and the moisture content of the pile body, turning the pile at the temperature of over 55 ℃, and supplementing water until the moisture content is lower than 35% to the moisture content of 50% -55%.
(4) And (4) repeating the process of the step (3), turning the pile once every 10 days when the temperature is lower than 55 ℃ again until the temperature is lower than 30 ℃ and the temperature does not rise any more after water replenishing and pile turning, and finishing the fermentation process.
Influence of carbon and nitrogen combined fixing agent on fermentation temperature
The addition amounts of the carbon-nitrogen combined fixing agent treated by T1, T2, T3 and T4 (the preparation process is shown in example 1, the raw material dosage is 10 percent of dilute phosphoric acid concentration, 350kg, 82 percent of attapulgite powder purity and 1000 kg) are respectively 0 percent, 5 percent, 10 percent and 15 percent of the dry weight of the waste biomass. The fermentation temperature changes in the test process are shown in figure 1 (Tc is local air temperature), and the fermentation temperature changes in a unimodal curve in the whole fermentation period. Within 9 days after composting began, the organic substances in the material were rapidly degraded by the microorganisms and heat was generated, and the fermentation temperature rapidly increased. All the fermentation temperature is raised to be more than 50 ℃ in 4 to 5 days after the composting starts, and is gradually reduced after the fermentation temperature is kept in a range of 50 to 70 ℃ for about 13 to 14 days. On the 25 th day after the start of composting, the fermentation temperature in each treatment was reduced to about 30 ℃ and remained substantially stable, at which time the decomposition was substantially complete. In the whole period of compost fermentation, each treatment is subjected to four periods of temperature rise, high temperature, temperature reduction and decomposition, and the high temperature period above 50 ℃ exceeds 10 d, which shows that the addition of the carbon-nitrogen combined fixing agent does not produce obvious negative effects on the fermentation, disinfection and sterilization effects of the organic fertilizer, but the highest temperature of T4 treatment is slightly higher than 50 ℃, so that the proper addition amount is 5-10%.
Influence of carbon and nitrogen combined fixing agent on carbon and nitrogen emission reduction effect
The organic carbon loss and the nitrogen loss of each treatment are in a descending trend along with the increase of the addition amount of the carbon and nitrogen combined fixing agent (figure 2), wherein the organic carbon loss rate of T1 is the largest, and the organic carbon loss rate of T4 is the smallest. The organic carbon loss rates of T1, T2, T3 and T4 treatment are respectively 51.84%, 42.56%, 40.12% and 37.25%, and the organic matter loss rates of T2, T3 and T4 are respectively 18%, 23% and 28% lower than those of the control. The nitrogen loss rate was reduced from 17.8% for T1 to 9.5%, 6.2% and 5.3% for T2, T3 and T4, respectively.
The sulfuric acid modified attapulgite is used for replacing the carbon-nitrogen combined fixing agent to perform a comparison experiment, and the loss rate of organic carbon and nitrogen in the organic fertilizer fermentation process is shown in figure 3. The organic carbon content of the treated attapulgite clay under the treatment of T1, T2, T3 and T4 is respectively 64.26%, 60.13%, 75.23% and 52.36%, the nitrogen loss rate of the treated attapulgite clay is respectively 28.9%, 21.4%, 16.2% and 12.2%, and the organic carbon and nitrogen loss rates of the treated attapulgite clay are obviously higher than that of the carbon and nitrogen combined fixing agent (different capital letters indicate that the difference between the sulfuric acid modified attapulgite clay and the carbon and nitrogen combined fixing agent is obvious, and different lowercase letters indicate that the difference between different application amounts of the sulfuric acid modified attapulgite clay or the carbon and nitrogen combined fixing agent is obvious), which indicates that the carbon and nitrogen combined fixing effect of the treated attapulgite clay is obviously higher than that of the sulfuric acid modified attapulgite clay.
Preparing a sulfuric acid modified attapulgite reference sample: crushing attapulgite clay (with the purity of 82 percent), sieving the crushed attapulgite clay with a 100-mesh sieve, adding the crushed attapulgite clay into a sulfuric acid solution with the concentration of 2mol/L, stirring the crushed attapulgite clay and the sulfuric acid solution at the room temperature for 3 hours, washing the crushed attapulgite clay and the sulfuric acid solution with distilled water until the pH value is 6, centrifuging the mixed solution, and drying a solid phase at the temperature of 60 ℃.
Organic carbon and carbon nitrogen analysis determination and loss rate calculation methods are described in the methods of Wang YuXuan, russian Yun Yuan Hua, yuanjin Hua and the like, the influence of attapulgite addition on the fermentation temperature and nutrients of organic fertilizers [ J ]. Agricultural environmental science report, 2021,40 (12): 2779-2787.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon-nitrogen combined fixing agent comprises the following steps:
(1) Mixing attapulgite and phosphoric acid for reaction until no bubbles are generated basically, and controlling the pH value at the end point of the reaction within 1-3;
(2) And after the reaction is finished, directly drying the attapulgite without washing to obtain the carbon-nitrogen combined fixing agent.
2. The method of claim 1, wherein: the phosphoric acid is 10 to 15wt% phosphoric acid aqueous solution, and the adding amount of the phosphoric acid is controlled to enable the attapulgite to be completely wet.
3. The method of claim 2, wherein: the mass ratio of the attapulgite to the phosphoric acid aqueous solution is 1.
4. The method of claim 1, wherein: the reaction temperature is 60 to 80 ℃.
5. The method of claim 1, wherein: drying until the water content of the carbon-nitrogen combined fixing agent is below 20 wt%.
6. The method of claim 1, wherein: the water content of the carbon and nitrogen combined fixing agent is 15-18 wt%.
7. A carbon and nitrogen combined fixative prepared according to the method of any one of claims 1-6.
8. Use of a carbon-nitrogen combined fixing agent as defined in claim 7 for the preparation of organic fertilizers.
9. Use according to claim 8, characterized in that: mixing and fermenting a biomass raw material and the carbon-nitrogen combined fixing agent as defined in claim 7 to obtain the organic fertilizer.
10. Use according to claim 9, characterized in that: the dosage of the carbon-nitrogen combined fixing agent is 5 to 10 percent of the dry weight of the biomass raw material.
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