Humic acid-containing water-soluble fertilizer based on breeding waste liquid and preparation method of humic acid-containing water-soluble fertilizer

Abstract

The invention relates to a humic acid-containing water-soluble fertilizer based on breeding waste liquid and a preparation method thereof, and belongs to the technical field of organic fertilizers. According to the invention, pig manure in a farm is used as a raw material to prepare a water-soluble fertilizer base solution, and the water-soluble fertilizer base solution is used to prepare a humic acid-containing aqueous solution based on breeding waste liquid. The method comprises the following steps: squeezing pig manure in a farm through a stacked screw machine to obtain a filtrate; filtering the filtrate through a screen, an automatic filter, a ceramic membrane and a nanofiltration membrane respectively to obtain a water-soluble fertilizer base solution; mixing the obtained water-soluble fertilizer base solution with mineral source fulvic acid, amide nitrogen, ammonium nitrogen, nitrate nitrogen, phosphorus, potassium oxide and a synergist to obtain a humic acid-containing aqueous solution based on the breeding waste liquid; according to the preparation method disclosed by the invention, the pig manure of a farm is reasonably utilized, the commercial fertilizer with high additional value is prepared, the economic and environment-friendly effects are realized, the prepared fertilizer contains a large number of nutrient elements required by crops, the effective time is lasting, and the water and fertilizer retention capability of soil can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic fertilizers, and in particular relates to a water-soluble fertilizer containing humic acid based on aquaculture waste liquid and a preparation method thereof. Background Art

[0002] Generally, the absorption rate of feed by pigs in farms is 30%-40%, which means that a large part of the nutrients in the feed are present in pig manure. The manure produced by farms is discharged into pig manure pools through special pipelines. At present, there are two main ways to dispose of manure.

[0003] The first treatment method is to treat it in accordance with traditional sewage treatment methods. After solid-liquid separation, the dry matter is made into fertilizer or directly returned to the field, and the liquid is treated physically, chemically, and biologically to meet the discharge standards. This treatment method has only input but no output, and the economic benefits are very poor.

[0004] The second treatment method is to send the aquaculture waste to a large biogas station. However, the construction of biogas stations is concentrated, and the surrounding waste liquid needs to be transported to the biogas station through pipelines or for centralized fermentation, which requires a lot of costs and has certain safety risks. After being transported to the biogas station, the filtrate is used for fermentation to produce biogas, and the filtered waste residue is directly returned to the field and used as a raw material for the production of solid organic fertilizer. However, the direct return of waste residue to the field may cause the deterioration of soil physical and chemical indicators, aggravate soil acidification, inhibit crop growth, increase pests and diseases, cause eutrophication pollution of water bodies, and greatly increase the emission of methane gas with extremely high greenhouse effect. This treatment method is not conducive to environmental protection, and the economic benefits are also poor. Based on this, the present invention provides a humic acid-containing water-soluble fertilizer based on aquaculture waste liquid and a preparation method thereof. Summary of the invention

[0005] The object of the present invention is to provide a water-soluble fertilizer containing humic acid based on aquaculture waste liquid and a preparation method thereof, so as to solve the problems mentioned in the above background technology.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A humic acid-containing water-soluble fertilizer based on aquaculture waste liquid, comprising the following raw materials: pig manure from a farm, mineral humic acid, amide nitrogen, ammonium nitrogen, nitrate nitrogen, phosphorus, potassium oxide, and a synergist;

[0008] A method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid comprises the following steps:

[0009] The first step is to fully squeeze the pig manure from the farm through a snail press and then vibrate and filter to extract the manure filtrate;

[0010] The second step is to use a sewage pump with a blade to extract the feces filtrate, and filter it in turn through three sets of dual parallel automatic filters. The filter residue after each filtration can be re-discharged into the snail stacking machine in the first step. The filtrate obtained after three filtrations enters the filtrate storage tank for standby use;

[0011] The third step is to extract the filtrate from the filtrate storage tank with a centrifugal pump and filter it with a circulating filter pump. The filter screen used is a double parallel ceramic membrane. The filtered residue can be discharged back into the screw stacking machine in the first step, and the filtrate obtained by filtration enters the ceramic membrane storage tank;

[0012] Step 4: Use a centrifugal pump to extract the filtrate from the ceramic membrane storage tank and use a high-pressure pump to pressurize and filter. The filter screen used is a nanofiltration membrane. The concentrated liquid after separation is the water-soluble fertilizer base liquid.

[0013] The fifth step is to mix the water-soluble fertilizer base liquid, mineral humic acid, amide nitrogen, ammonium nitrogen, nitrate nitrogen, phosphorus, potassium oxide and synergist to obtain a water-soluble fertilizer containing humic acid based on aquaculture waste liquid.

[0014] Furthermore, the sieve size used in the first step is 120 mesh.

[0015] Furthermore, the screen used in the first group of filters in the second step is 400 mesh, the screen used in the second group of filters is 800 mesh, and the screen used in the third group of filters is 1000 mesh.

[0016] Furthermore, in the third step, the power of the centrifugal pump is 5.5 kW, the flow rate is 32 m³ / h, the power of the circulating filtration pump is 37 kW, the flow rate is 350 m³ / h, and the specification of the ceramic membrane is 200 nanometers.

[0017] Furthermore, in the fourth step, the power of the centrifugal pump is 3 kW, the flow rate is 15 m³ / h, the power of the high-pressure pump is 15 kW, the flow rate is 15 m³ / h, and the specification of the nanofiltration membrane is 5 nanometers.

[0018] Furthermore, the amide nitrogen is urea, the ammonium nitrogen is one of ammonium sulfate and ammonium chloride, the nitrate nitrogen is potassium nitrate, and the phosphorus is monoammonium phosphate.

[0019] Furthermore, in the fifth step, the mass proportions of each raw material are 60-65 parts of water-soluble fertilizer base liquid, 3-6 parts of mineral humic acid, 10-16 parts of amide nitrogen, 5-8 parts of ammonium nitrogen, 3-5 parts of nitrate nitrogen, 2.5-5 parts of phosphorus, 2-3 parts of potassium oxide, and 0.6-1 parts of enhancer.

[0020] Further, the synergist is prepared by the following steps:

[0021] Step 1, salicylaldehyde, ethyl acetoacetate, diethylamine and chloroform were mixed in a three-necked flask under ice-water bath conditions, magnetic stirring was turned on, and the mixture was reacted for 1-2 hours under ice-water bath conditions. After the reaction was completed, the organic layer was separated with a separatory funnel, the solvent was removed by rotary evaporation of the organic layer, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 1;

[0022] Step 2, intermediate 1, 3,4-dimethyl-1H-pyrazole and N,N-dimethylformamide were mixed in a three-necked flask, equipped with a condenser and a thermometer, and magnetic stirring was turned on. The mixture was reacted at 120-130°C for 6-8h. After the reaction was completed, the solvent was removed by rotary evaporation, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 2;

[0023] Step 3, under ice-water bath conditions, phosphorus trichloride and toluene are mixed in a three-necked flask, a condenser and a thermometer are installed, magnetic stirring is turned on, and nitrogen is introduced to exhaust the air in the three-necked flask, and then the toluene solution of intermediate 2 is added dropwise to the three-necked flask. After the addition is completed, ammonia is continuously introduced into the three-necked flask, and the reaction is carried out under ice-water bath conditions for 2 hours, and then the ice-water bath is removed, and the reaction is continued at room temperature for 1 hour. After the reaction is completed, the system temperature is raised to 55-65° C., and the filtrate is filtered while hot. The obtained filtrate is recrystallized and dried to obtain the synergist.

[0024] Furthermore, the amount ratio of salicylaldehyde, ethyl acetoacetate, diethylamine and chloroform used in step 1 is 0.1 mol: 0.1 mol: 0.03-0.04 mol: 60-80 mL.

[0025] Furthermore, the usage ratio of the intermediate 1, 3,4-dimethyl-1H-pyrazole and N,N-dimethylformamide used in step 2 is 0.07 mol: 0.1-0.12 mol: 60-80 mL.

[0026] Furthermore, the toluene solution of intermediate 2 in step 3 is prepared from 0.04 mol of intermediate 2 and 100 mL of toluene.

[0027] Furthermore, the usage ratio of trichlorothiophosphorus, toluene, and toluene solution of intermediate 2 used in step 3 is 0.04 mol:80 mL:100.49 g.

[0028] Beneficial effects of the present invention:

[0029] 1) The present invention uses pig manure from a breeding farm as a raw material to prepare a water-soluble fertilizer base liquid, and uses the water-soluble fertilizer base liquid to prepare a humic acid-containing aqueous solution based on breeding waste liquid. The present invention first squeezes the pig manure from the breeding farm through a screw stacker to obtain a filtrate, and then filters the filtrate through a screen, an automatic filter, a ceramic membrane, and a nanofiltration membrane to obtain a water-soluble fertilizer base liquid, and then mixes the obtained water-soluble fertilizer base liquid with mineral fulvic acid, amide nitrogen, ammonium nitrogen, nitrate nitrogen, phosphorus, potassium oxide, and a synergist to obtain a humic acid-containing aqueous solution based on breeding waste liquid; the water-soluble fertilizer base liquid prepared by the present invention contains a large amount of nutrient elements required by crops, can improve the water and fertilizer retention capacity of the soil, and fully activate the soil, and is added with mineral fulvic acid with good adsorption and chelating properties, which can form a stable complex with the soil and fix the nutrients in the soil. The active substances in the mineral fulvic acid can also stimulate the cell division and growth of crops and increase the chlorophyll content in plants.

[0030] 2) The present invention uses salicylaldehyde and ethyl acetoacetate as raw materials, and uses the aldehyde group of salicylaldehyde and the active methylene group of ethyl acetoacetate to undergo Knoevenagel reaction dehydration condensation under the catalysis of diethylamine to obtain intermediate 1, and then uses intermediate 1 as a raw material, and uses the double bond of intermediate 1 to react with the imino group of 3,4-dimethyl-1H-pyrazole to undergo Michael addition reaction to obtain intermediate 2, wherein 3,4-dimethyl-1H-pyrazole serves as both a reaction raw material and a catalyst, and finally uses intermediate 2 as a raw material, uses the phenolic hydroxyl group of intermediate 2 to react with trichlorothiophosphate to undergo esterification reaction, and then reacts with ammonia to undergo substitution reaction. The reaction obtains an enhancer with a thiophosphoramide structure; the enhancer of the invention has a thiophosphoramide structure, can inhibit the action of soil urease, slow down the hydrolysis loss of urea, and improve the utilization rate of nitrogen in urea; the pyrazole structure in the enhancer can effectively inhibit the action of nitrifying bacteria in the soil, slow down the decomposition loss of ammonium roots in the soil, and improve the utilization rate of nitrogen in ammonium salts; the combination of the two effects can greatly improve the utilization rate of fertilizers; in addition, the enhancer of the invention also has stable benzene rings and ester groups, is not easy to volatilize, and is not easy to decompose in an alkaline environment, so it can be effective for a long time. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] A synergist is prepared by the following steps:

[0034] Step 1, 0.1 mol of salicylaldehyde, 0.1 mol of ethyl acetoacetate, 0.03 mol of diethylamine and 60 mL of chloroform were mixed in a three-necked flask under ice-water bath conditions, magnetic stirring was turned on, and the mixture was reacted under ice-water bath conditions for 1 h. After the reaction was completed, the organic layer was separated with a separatory funnel, the solvent was removed by rotary evaporation of the organic layer, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 1;

[0035] Step 2, 0.07 mol of intermediate 1, 0.1 mol of 3,4-dimethyl-1H-pyrazole and 60 mL of N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 120°C for 6 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 2;

[0036] Step 3, under ice-water bath conditions, 0.04 mol of trichlorothiophosphorus and 80 mL of toluene were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and nitrogen was introduced to exhaust the air in the three-necked flask, and then 100.49 g of a solution prepared by 0.04 mol of intermediate 2 and 100 mL of toluene was added dropwise to the three-necked flask. After the addition was completed, ammonia was continuously introduced into the three-necked flask, and the reaction was carried out under ice-water bath conditions for 2 h, and then the ice-water bath was removed, and the reaction was continued at room temperature for 1 h. After the reaction was completed, the system temperature was raised to 55 ° C, filtered while hot, and the obtained filtrate was recrystallized and dried to obtain the synergist.

[0037] Example 2

[0038] A synergist is prepared by the following steps:

[0039] Step 1, 0.1 mol of salicylaldehyde, 0.1 mol of ethyl acetoacetate, 0.035 mol of diethylamine and 70 mL of chloroform were mixed in a three-necked flask under ice-water bath conditions, magnetic stirring was turned on, and the mixture was reacted for 1.5 h under ice-water bath conditions. After the reaction was completed, the organic layer was separated with a separatory funnel, the solvent was removed by rotary evaporation of the organic layer, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 1;

[0040] Step 2, 0.07 mol of intermediate 1, 0.11 mol of 3,4-dimethyl-1H-pyrazole and 70 mL of N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 125°C for 7 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 2;

[0041] Step 3, under ice-water bath conditions, 0.04 mol of trichlorothiophosphorus and 80 mL of toluene were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and nitrogen was introduced to exhaust the air in the three-necked flask, and then 100.49 g of a solution prepared by 0.04 mol of intermediate 2 and 100 mL of toluene was added dropwise to the three-necked flask. After the addition was completed, ammonia was continuously introduced into the three-necked flask, and the reaction was carried out under ice-water bath conditions for 2 h, and then the ice-water bath was removed, and the reaction was continued at room temperature for 1 h. After the reaction was completed, the system temperature was raised to 60 ° C, filtered while hot, and the obtained filtrate was recrystallized and dried to obtain the synergist.

[0042] Example 3

[0043] A synergist is prepared by the following steps:

[0044] Step 1, 0.1 mol of salicylaldehyde, 0.1 mol of ethyl acetoacetate, 0.04 mol of diethylamine and 80 mL of chloroform were mixed in a three-necked flask under ice-water bath conditions, magnetic stirring was turned on, and the mixture was reacted for 2 h under ice-water bath conditions. After the reaction was completed, the organic layer was separated with a separatory funnel, the solvent was removed by rotary evaporation of the organic layer, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 1;

[0045] Step 2, 0.07 mol of intermediate 1, 0.12 mol of 3,4-dimethyl-1H-pyrazole and 80 mL of N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the reaction was carried out at a temperature of 130°C for 8 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the remaining solid was subjected to silica gel column chromatography to obtain intermediate 2;

[0046] Step 3, under ice-water bath conditions, 0.04 mol of trichlorothiophosphorus and 80 mL of toluene were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and nitrogen was introduced to exhaust the air in the three-necked flask, and then 100.49 g of a solution prepared by 0.04 mol of intermediate 2 and 100 mL of toluene was added dropwise to the three-necked flask. After the addition was completed, ammonia was continuously introduced into the three-necked flask, and the reaction was carried out under ice-water bath conditions for 2 h, and then the ice-water bath was removed, and the reaction was continued at room temperature for 1 h. After the reaction was completed, the system temperature was raised to 65 ° C, filtered while hot, and the obtained filtrate was recrystallized and dried to obtain the synergist.

[0047] Example 4

[0048] A humic acid-containing water-soluble fertilizer based on aquaculture waste liquid, comprising the following raw materials: pig manure from a farm, mineral-source humic acid, urea, ammonium sulfate, potassium nitrate, monoammonium phosphate, potassium oxide, and the synergist obtained in Example 1;

[0049] A method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid comprises the following steps:

[0050] The first step is to fully squeeze the pig manure from the farm through a snail press and then use a 120-mesh screen to vibrate and filter to extract the manure filtrate;

[0051] The second step is to use a sewage pump with a blade to extract the fecal filtrate, and filter it in turn through three sets of dual parallel automatic filters. The screen used in the first set of filters is 400 mesh, the screen used in the second set of filters is 800 mesh, and the screen used in the third set of filters is 1000 mesh. The filter residue after each filtration can be re-discharged into the spiral stacking machine in the first step. The filtrate obtained after three filtrations enters the filtrate storage tank for standby use;

[0052] Step 3: Use a 5.5kW centrifugal pump to extract filtrate from the filtrate storage tank at a flow rate of 32m³ / h and use a 37kW circulating filter pump to pressurize and filter at a flow rate of 350m³ / h. The filter screen used is a double parallel 200 nanometer ceramic membrane. The filtered residue can be re-discharged into the screw stacking machine in the first step, and the filtered filtrate enters the ceramic membrane storage tank;

[0053] Step 4: Use a 3kW centrifugal pump to extract the filtrate from the ceramic membrane storage tank at a flow rate of 15m³ / h and use a 15kW high-pressure pump to pressurize and filter at a flow rate of 15m³ / h. The filter used is a 5-nanometer nanofiltration membrane. The concentrated liquid after separation is the water-soluble fertilizer base liquid.

[0054] The fifth step is to mix 60 parts of water-soluble fertilizer base liquid, 3 parts of mineral humic acid, 10 parts of urea, 5 parts of ammonium sulfate, 3 parts of potassium nitrate, 2.5 parts of monoammonium phosphate, 2 parts of potassium oxide, and 0.6 parts of the synergist obtained in Example 1 to obtain a water-soluble fertilizer containing humic acid based on aquaculture waste liquid.

[0055] Example 5

[0056] A humic acid-containing water-soluble fertilizer based on aquaculture waste liquid, comprising the following raw materials: pig manure from a farm, mineral humic acid, urea, ammonium sulfate, potassium nitrate, monoammonium phosphate, potassium oxide, and the synergist obtained in Example 2;

[0057] A method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid comprises the following steps:

[0058] The first step is to fully squeeze the pig manure from the farm through a snail press and then use a 120-mesh screen to vibrate and filter to extract the manure filtrate;

[0059] The second step is to use a sewage pump with a blade to extract the fecal filtrate, and filter it in turn through three sets of dual parallel automatic filters. The screen used in the first set of filters is 400 mesh, the screen used in the second set of filters is 800 mesh, and the screen used in the third set of filters is 1000 mesh. The filter residue after each filtration can be re-discharged into the spiral stacking machine in the first step. The filtrate obtained after three filtrations enters the filtrate storage tank for standby use;

[0060] Step 3: Use a 5.5kW centrifugal pump to extract filtrate from the filtrate storage tank at a flow rate of 32m³ / h and use a 37kW circulating filter pump to pressurize and filter at a flow rate of 350m³ / h. The filter screen used is a double parallel 200 nanometer ceramic membrane. The filtered residue can be re-discharged into the screw stacking machine in the first step, and the filtered filtrate enters the ceramic membrane storage tank;

[0061] Step 4: Use a 3kW centrifugal pump to extract the filtrate from the ceramic membrane storage tank at a flow rate of 15m³ / h and use a 15kW high-pressure pump to pressurize and filter at a flow rate of 15m³ / h. The filter used is a 5-nanometer nanofiltration membrane. The concentrated liquid after separation is the water-soluble fertilizer base liquid.

[0062] The fifth step is to mix 62 parts of water-soluble fertilizer base liquid, 4 parts of mineral humic acid, 13 parts of urea, 6 parts of ammonium sulfate, 4 parts of potassium nitrate, 3.7 parts of monoammonium phosphate, 2.5 parts of potassium oxide, and 0.8 parts of the synergist obtained in Example 2 to obtain a water-soluble fertilizer containing humic acid based on aquaculture waste liquid.

[0063] Example 6

[0064] A humic acid-containing water-soluble fertilizer based on aquaculture waste liquid, comprising the following raw materials: pig manure from a farm, mineral humic acid, urea, ammonium chloride, potassium nitrate, monoammonium phosphate, potassium oxide, and the synergist obtained in Example 3;

[0065] A method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid comprises the following steps:

[0066] The first step is to fully squeeze the pig manure from the farm through a snail press and then use a 120-mesh screen to vibrate and filter to extract the manure filtrate;

[0067] The second step is to use a sewage pump with a blade to extract the fecal filtrate, and filter it in turn through three sets of dual parallel automatic filters. The screen used in the first set of filters is 400 mesh, the screen used in the second set of filters is 800 mesh, and the screen used in the third set of filters is 1000 mesh. The filter residue after each filtration can be re-discharged into the spiral stacking machine in the first step. The filtrate obtained after three filtrations enters the filtrate storage tank for standby use;

[0068] Step 3: Use a 5.5kW centrifugal pump to extract filtrate from the filtrate storage tank at a flow rate of 32m³ / h and use a 37kW circulating filter pump to pressurize and filter at a flow rate of 350m³ / h. The filter screen used is a double parallel 200 nanometer ceramic membrane. The filtered residue can be re-discharged into the screw stacking machine in the first step, and the filtered filtrate enters the ceramic membrane storage tank;

[0069] Step 4: Use a 3kW centrifugal pump to extract the filtrate from the ceramic membrane storage tank at a flow rate of 15m³ / h and use a 15kW high-pressure pump to pressurize and filter at a flow rate of 15m³ / h. The filter used is a 5-nanometer nanofiltration membrane. The concentrated liquid after separation is the water-soluble fertilizer base liquid.

[0070] The fifth step is to mix 65 parts of water-soluble fertilizer base liquid, 6 parts of mineral humic acid, 16 parts of urea, 8 parts of ammonium chloride, 5 parts of potassium nitrate, 5 parts of monoammonium phosphate, 3 parts of potassium oxide, and 1 part of the synergist obtained in Example 3 to obtain a water-soluble fertilizer containing humic acid based on aquaculture waste liquid.

[0071] Comparative Example 1

[0072] A humic acid-containing water-soluble fertilizer based on aquaculture wastewater, comprising the following raw materials: pig manure from a farm, mineral-source humic acid, urea, ammonium chloride, potassium nitrate, monoammonium phosphate, and potassium oxide;

[0073] A method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid comprises the following steps:

[0074] The first step is to fully squeeze the pig manure from the farm through a snail press and then use a 120-mesh screen to vibrate and filter to extract the manure filtrate;

[0075] The second step is to use a sewage pump with a blade to extract the fecal filtrate, and filter it in turn through three sets of dual parallel automatic filters. The screen used in the first set of filters is 400 mesh, the screen used in the second set of filters is 800 mesh, and the screen used in the third set of filters is 1000 mesh. The filter residue after each filtration can be re-discharged into the spiral stacking machine in the first step. The filtrate obtained after three filtrations enters the filtrate storage tank for standby use;

[0076] Step 3: Use a 5.5kW centrifugal pump to extract filtrate from the filtrate storage tank at a flow rate of 32m³ / h and use a 37kW circulating filter pump to pressurize and filter at a flow rate of 350m³ / h. The filter screen used is a double parallel 200 nanometer ceramic membrane. The filtered residue can be re-discharged into the screw stacking machine in the first step, and the filtered filtrate enters the ceramic membrane storage tank;

[0077] Step 4: Use a 3kW centrifugal pump to extract the filtrate from the ceramic membrane storage tank at a flow rate of 15m³ / h and use a 15kW high-pressure pump to pressurize and filter at a flow rate of 15m³ / h. The filter used is a 5-nanometer nanofiltration membrane. The concentrated liquid after separation is the water-soluble fertilizer base liquid.

[0078] The fifth step is to mix 65 parts of water-soluble fertilizer base liquid, 6 parts of mineral humic acid, 16 parts of urea, 8 parts of ammonium chloride, 5 parts of potassium nitrate, 5 parts of monoammonium phosphate, and 3 parts of potassium oxide to obtain a water-soluble fertilizer containing humic acid based on aquaculture waste liquid.

[0079] Comparative Example 2

[0080] This comparative example is a commercially available water-soluble compound fertilizer.

[0081] Five corn planting groups were designed using land with the same soil fertility. Each group was a square area of ​​5m long and 5m wide, with a total area of ​​25m 2 Each group planted an equal number of corn plants and applied a humic acid-containing water-soluble fertilizer based on aquaculture waste liquid and a commercially available water-soluble compound fertilizer in Examples 4-6 and Comparative Example 1, respectively, at an application rate of 0.1 kg / m 2 , recorded the average plant height, average ear length, average ear weight, average 100-grain weight of corn, and tested the average sugar content. The results are shown in Table 1: Table 1

[0082]

[0083] It can be seen from Table 1 that the growth state, fruit weight and sugar content of the corn plants applied with a water-soluble fertilizer containing humic acid based on aquaculture waste liquid in Examples 4-6 of the present invention are better than those of the corn plants applied with commercially available water-soluble compound fertilizers, while the growth and fruit quality of the corn plants in Comparative Example 1 are not as good as those of the corn plants in Examples 4-6. The reason is that the synergist of the present invention is not added to the fertilizer, resulting in the premature failure of the nitrogen in the fertilizer. In summary, the water-soluble compound fertilizer containing humic acid based on aquaculture waste liquid of the present invention can effectively improve soil fertility, and the nitrogen in the fertilizer has a long effective time and a high fertilizer utilization rate, and can be widely used in the field of agricultural planting.

[0084] The above is a detailed introduction to a water-soluble fertilizer containing humic acid based on aquaculture waste liquid and a preparation method thereof provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enables any technician in the field to practice the present invention, including the manufacture and use of any device or system, and the implementation of any combination method. It should be pointed out that for ordinary technicians in the technical field, the present invention can also be improved and modified without departing from the principle of the present invention. In particular, as long as there is no structural conflict, the various features in the embodiments disclosed in the present invention can be used in combination with each other in any way. The fact that these combinations are not exhaustively described in this specification is only for the purpose of omitting space and saving resources. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A water-soluble fertilizer containing humic acid based on aquaculture waste liquid, characterized in that: Including the following raw materials: pig manure from farms, mineral fulvic acid, amide nitrogen, ammonium nitrogen, nitrate nitrogen, phosphorus, potassium oxide, synergist; Wherein, the synergist is prepared by the following steps: Step 1, salicylaldehyde, ethyl acetoacetate, diethylamine and chloroform are mixed in a container under ice-water bath conditions, stirred evenly, and reacted under ice-water bath conditions for 1-2 hours to obtain intermediate 1; Step 2, intermediate 1, 3,4-dimethyl-1H-pyrazole and N,N-dimethylformamide are mixed in a container, stirred evenly, and reacted at a temperature of 120-130° C. for 6-8 hours to obtain intermediate 2; Step 3, under ice-water bath conditions, trichlorothiophosphorus and toluene are mixed in a container, stirred evenly, and nitrogen is introduced to exhaust the air in the container, and then the toluene solution of intermediate 2 is added dropwise to the container. After the addition is completed, ammonia is continuously introduced into the container, and the reaction is carried out under ice-water bath conditions for 2 hours, and then the ice-water bath is removed, and the reaction is continued at room temperature for 1 hour to obtain the synergist.

2. A water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 1, characterized in that: The amount ratio of salicylaldehyde, ethyl acetoacetate, diethylamine and chloroform used in step 1 is 0.1 mol: 0.1 mol: 0.03-0.04 mol: 60-80 mL.

3. A water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 1, characterized in that: The usage ratio of the intermediate 1, 3,4-dimethyl-1H-pyrazole and N,N-dimethylformamide used in step 2 is 0.07 mol: 0.1-0.12 mol: 60-80 mL.

4. A water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 1, characterized in that: The toluene solution of intermediate 2 in step 3 is prepared from 0.04 mol of intermediate 2 and 100 mL of toluene.

5. A water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 1, characterized in that: The amount ratio of trichlorothiophosphorus, toluene and toluene solution of intermediate 2 used in step 3 is 0.04 mol:80 mL:100.49 g.

6. A method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to any one of claims 1 to 5, characterized in that: The method comprises the following preparation steps: The first step is to fully squeeze the pig manure from the farm through a snail press and then vibrate and filter to extract the manure filtrate; The second step is to use a sewage pump with a blade to extract the feces filtrate, and filter it in turn through three sets of dual parallel automatic filters. The filter residue after each filtration can be re-discharged into the snail stacking machine in the first step. The filtrate obtained after three filtrations enters the filtrate storage tank for standby use; The third step is to extract the filtrate from the filtrate storage tank with a centrifugal pump and filter it with a circulating filter pump. The filter screen used is a double parallel ceramic membrane. The filtered residue can be discharged back into the screw stacking machine in the first step, and the filtrate obtained by filtration enters the ceramic membrane storage tank; Step 4: Use a centrifugal pump to extract the filtrate from the ceramic membrane storage tank and use a high-pressure pump to pressurize and filter. The filter screen used is a nanofiltration membrane. The concentrated liquid after separation is the water-soluble fertilizer base liquid. The fifth step is to mix the water-soluble fertilizer base liquid, mineral humic acid, amide nitrogen, ammonium nitrogen, nitrate nitrogen, phosphorus, potassium oxide and synergist to obtain a water-soluble fertilizer containing humic acid based on aquaculture waste liquid.

7. The method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 6, characterized in that: The mesh size used in the first step is 120 mesh; the mesh used in the first set of filters in the second step is 400 mesh, the mesh used in the second set of filters is 800 mesh, and the mesh used in the third set of filters is 1000 mesh.

8. The method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 6, characterized in that: In the third step, the power of the centrifugal pump is 5.5kW, the flow rate is 32m³ / h, the power of the circulating filtration pump is 37kW, the flow rate is 350m³ / h, and the specification of the ceramic membrane is 200 nanometers; in the fourth step, the power of the centrifugal pump is 3kW, the flow rate is 15m³ / h, the power of the high-pressure pump is 15kW, the flow rate is 15m³ / h, and the specification of the nanofiltration membrane is 5 nanometers.

9. The method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 6, characterized in that: The amide nitrogen is urea, the ammonium nitrogen is one of ammonium sulfate and ammonium chloride, the nitrate nitrogen is potassium nitrate, and the phosphorus is monoammonium phosphate.

10. The method for preparing a water-soluble fertilizer containing humic acid based on aquaculture waste liquid according to claim 6, characterized in that: In the fifth step, the mass proportions of the raw materials are 60-65 parts of water-soluble fertilizer base liquid, 3-6 parts of mineral humic acid, 10-16 parts of amide nitrogen, 5-8 parts of ammonium nitrogen, 3-5 parts of nitrate nitrogen, 2.5-5 parts of phosphorus, 2-3 parts of potassium oxide, and 0.6-1 parts of enhancer.

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