CN113943195A

CN113943195A - Method for preparing organic carbon nutrient by using alcohol processing waste liquid

Info

Publication number: CN113943195A
Application number: CN202111172451.XA
Authority: CN
Inventors: 李英华; 邵泽强; 王涵博; 步欣潼
Original assignee: Jilin Institute of Chemical Technology
Current assignee: Jilin Institute of Chemical Technology
Priority date: 2021-10-08
Filing date: 2021-10-08
Publication date: 2022-01-18

Abstract

The invention discloses a method for preparing an organic carbon nutrient by using alcohol processing waste liquid, which specifically comprises the following steps: (1) adding an acid regulator into the alcohol processing waste liquid, then heating and stirring, and naturally cooling to obtain a solution A; (2) adding major elements, medium elements and trace elements into the solution A to obtain a solution B; (3) adding an acid-base blender into the solution B to obtain a solution C; (4) and filtering, concentrating and performing microwave radiation on the solution C to obtain the organic carbon nutrient. According to the invention, the organic carbon nutrient is prepared by taking the alcohol processing waste liquid as the raw material, so that on one hand, the alcohol processing waste liquid is reasonably utilized, and the resource waste and the environmental pollution are reduced; on the other hand, the organic carbon nutrient prepared by the method has rich organic carbon content and is rich in various elements required by plant growth, and after the organic carbon nutrient is used, the carbon-nitrogen ratio of soil can be improved, so that the utilization rate of a chemical fertilizer and the comprehensive effect generated by improving the soil are improved.

Description

Method for preparing organic carbon nutrient by using alcohol processing waste liquid

Technical Field

The invention relates to the technical field of recycling of alcohol processing waste liquid and preparation of an organic carbon nutrient, in particular to a method for preparing the organic carbon nutrient by using the alcohol processing waste liquid.

Background

Carbon plays an important role in the soil ecosystem and is a basic element required by plants. The conventional measure of carbon supplement is to apply enough organic fertilizer, but the organic fertilizer is slow-release fertilizer, although the organic matter content is high, most of the organic fertilizer cannot be dissolved in water in a short period, but exists in the form of humus, and water-soluble carbon can be gradually released only by long-time decomposition of soil microorganisms. Moreover, the organic fertilizer has low fertility and large dosage, is limited by raw materials and transportation cost (or transportation difficulty), and can not be applied or applied sufficiently in a large amount of cultivated land, thereby influencing the enthusiasm of farmers for use and the marketization of organic fertilizer products.

The organic carbon refers to organic compounds which are highly water-soluble and easily absorbed by plants, such as sugar, alcohol, acid, aldehyde and the like, and includes not only nitrogen-containing organic carbon nutrients (such as amino acid) but also nitrogen-free carbon nutrients. The key characteristics are two points: firstly, water solubility determines the effectiveness of the plant, namely whether the plant can absorb the plant or not; secondly, the type and the amount of the functional groups determine the fertilizer efficiency. Water solubility is the most basic condition for plant nutrition, and water insolubility is not absorbed by crops and cannot be called nutrition. Common organic matters are insoluble and mainly used for soil improvement instead of plant nutrition. The organic carbon fertilizer is a novel fertilizer, is prepared by controllably degrading high-concentration organic wastewater through a biochemical method and releasing a large amount of micromolecular water-soluble organic carbon, and can be directly utilized by the roots of plants. The organic carbon fertilizer has the outstanding fertilizer effect advantages that the fertilizer does not contain N, P, K and medium and trace mineral nutrients, but contains special organic carbon components, particularly cyclic and chain structures with complex structures and obvious physiological functions and groups such as acid, alcohol, aldehyde and the like, which are inherent reasons of the growth-promoting and stress-resisting functions.

The waste liquid after the alcohol fermentation process contains higher nutrient substances, such as protein, fiber, fat, sugar and other organic components, and the content is as high as 13.4%. If the macromolecular insoluble organic substances in the alcohol processing waste liquid are extracted and decomposed into micromolecular soluble substances, the organic carbon fertilizer can be processed into organic carbon fertilizer which can be directly absorbed and utilized by plants and soil.

By combining the current market situation of the liquid organic carbon fertilizer in China, if the alcohol processing waste liquid can be processed into the organic carbon nutrient, the added value of the product can be greatly improved, and the organic carbon nutrient has great market application prospect.

Disclosure of Invention

In view of the above, the present invention provides a method for preparing an organic carbon nutrient from an alcohol processing waste liquid, so as to solve the defects in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for preparing an organic carbon nutrient by using alcohol processing waste liquid specifically comprises the following steps:

(1) adding an acid regulator into the alcohol processing waste liquid, then heating and stirring, and naturally cooling to obtain a solution A;

(2) adding major elements, medium elements and trace elements into the solution A to obtain a solution B;

(3) adding an acid-base blender into the solution B to obtain a solution C;

(4) and filtering, concentrating and performing microwave radiation on the solution C to obtain the organic carbon nutrient.

Further, in the step (1), the acidic indicator is at least one of sulfuric acid, nitric acid and phosphoric acid, and is added to the alcohol processing waste liquid until the pH value is 1-2; the temperature of the heating and stirring is 90-95 ℃, the rotating speed is 100-; furthermore, the temperature of the heating and stirring is 95 ℃, the rotating speed is 180r/min, and the time is 8 h.

The method has the advantages that acid hydrolysis is carried out on the alcohol processing waste liquid by adding the acid regulators such as sulfuric acid, nitric acid and phosphoric acid, organic macromolecular groups in the alcohol processing waste liquid can be rapidly cracked into small molecular groups in the stirring process, the small molecular groups can be rapidly dissolved in water and diffused and permeated, and the organic matter is easily absorbed by crops and soil microorganisms.

Further, in the step (2), the macroelements are at least one of urea, potassium nitrate, ammonium dihydrogen phosphate and potassium dihydrogen phosphate and ammonium sulfate; the secondary element is chelated calcium EDCA-10 and/or magnesium sulfate; the trace element is at least one of chelated iron, boric acid, chelated manganese, chelated copper, chelated zinc, chelated molybdenum and chelated cobalt.

The further technical scheme has the advantages that the selected macroelements can supply energy for the basic growth of plants; the selected medium elements can stabilize the structure of the biological membrane, maintain the integrity of cells and promote the photosynthesis and the elongation of the cells of plants, thereby accelerating the growth of roots; the selected trace elements can enhance the photosynthesis and respiration of plants and enhance the stress resistance of the plants.

Further, in the step (3), an acid-base blender is added to the solution B to have a pH of 5 to 8.

The organic carbon nutrient has the beneficial effects that the organic carbon nutrient can play a better role in soil by adding the acid-base blender.

Further, in the step (4), the concentration is carried out until the total organic carbon content in the solution C is 5 to 12 percent; the power of the microwave radiation is 2-6kW, and the time is 2-4 h.

The beneficial effect of adopting the further technical scheme is that the content of the effective components of the organic carbon nutrient can be improved through concentration; the invention can remove harmful components in the organic carbon nutrient through microwave radiation, thereby improving the quality of the organic carbon nutrient.

According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:

according to the invention, the organic carbon nutrient is prepared by taking the alcohol processing waste liquid as the raw material, so that on one hand, the alcohol processing waste liquid is reasonably utilized, and the resource waste and the environmental pollution are reduced; on the other hand, the organic carbon nutrient prepared by the method has rich organic carbon content and is rich in various elements required by plant growth, and after the organic carbon nutrient is used, the carbon-nitrogen ratio of soil can be improved, so that the utilization rate of a chemical fertilizer and the comprehensive effect generated by improving the soil are improved.

Drawings

FIG. 1 shows the effect of the reaction temperature t on the extraction efficiency eta;

fig. 2 shows the effect of the reaction time T and pH on the extraction efficiency η (curves from top to bottom are pH 1, pH 2 and pH 3, respectively);

FIG. 3 is the effect of extraction reagents on extraction efficiency η;

FIG. 4 shows the alcohol processing waste liquid of example 1;

FIG. 5 is the organic carbon nutrient of example 1;

FIG. 6 is a pre-test graph of a potted test pakchoi (1-7 groups from left to right);

FIG. 7 is the fresh weight data of pakchoi in each test group of the potting test;

FIG. 8 is the fresh weight data of pakchoi in each test group of the potting test;

FIG. 9 is leaf length data of pakchoi in each test group of the potting test;

FIG. 10 is a pre-test plot of group 1 Brassica oleracea in a field trial;

FIG. 11 is a leaf length test chart of

field test group

1 and 4 pakchoi.

FIG. 12 shows the plant height H data of the small tomatoes of each test group in the pot experiment;

FIG. 13 is data of column diameter D of small tomatoes from each test group in a pot test;

FIG. 14 is SPAD-u data for small tomatoes from each test group of a pot test;

FIG. 15 is SPAD-m data for small tomatoes of each test group of a pot test;

FIG. 16 is SPAD-d data for small tomatoes from each test group of a pot test;

FIG. 17 is the above-ground fresh weight data for the small tomatoes of each test group of the pot test;

FIG. 18 is the above-ground dry weight data for the small tomatoes of each test group of the pot test;

FIG. 19 is the yield data of small tomatoes from each test group of the pot experiment.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The method for preparing the organic carbon nutrient by utilizing the alcohol processing waste liquid specifically comprises the following steps:

(1) adding sulfuric acid into the alcohol processing waste liquid until the pH value is 1, then heating to 95 ℃, stirring at the rotating speed of 180r/min for 8 hours, and naturally cooling to obtain a solution A;

wherein, the macroelements are urea, potassium nitrate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium sulfate, the secondary elements are chelated calcium EDCA-10 and magnesium sulfate, and the trace elements are chelated iron, boric acid, chelated manganese, chelated copper, chelated zinc, chelated molybdenum and chelated cobalt;

(3) adding an acid-base blender into the solution B until the pH value is 6.8 to obtain a solution C;

(4) and filtering the solution C, concentrating until the total organic carbon content is 4%, and performing microwave radiation for 3 hours at the power of 4kW to obtain the organic carbon nutrient.

Example 2

(1) adding nitric acid into the alcohol processing waste liquid until the pH value is 1, then heating to 90 ℃, stirring at the rotating speed of 100r/min for 8 hours, and naturally cooling to obtain a solution A;

(3) adding an acid-base blender to the solution B until the pH value is 5 to obtain a solution C;

(4) and filtering the solution C, concentrating until the total organic carbon content is 5%, and performing microwave radiation for 4 hours at the power of 2kW to obtain the organic carbon nutrient.

Example 3

(1) adding phosphoric acid into the alcohol processing waste liquid until the pH value is 2, then heating to 95 ℃, stirring at the rotating speed of 200r/min for 6 hours, and naturally cooling to obtain a solution A;

(3) adding an acid-base blender to the solution B until the pH value is 8 to obtain a solution C;

(4) and filtering the solution C, concentrating until the total organic carbon content is 12%, and performing microwave radiation for 2 hours at the power of 6kW to obtain the organic carbon nutrient.

Performance testing

First, study of experiments

1. Influence of the reaction temperature T

The original pH (3.25) of the alcohol processing waste liquid is not changed, the reaction time is fixed to be 8h, the reaction temperature is changed, the alcohol processing waste liquid is extracted respectively, the corresponding extraction efficiency is calculated, and data mapping is obtained. The results are shown in FIG. 1.

FIG. 1 shows the effect of the reaction temperature T on the extraction efficiency eta. As can be seen from fig. 1, the extraction efficiency η gradually increases with the increase of the temperature T, but the energy consumption increases with the increase of the temperature, so that the temperature condition is fixed at 95 ℃ for the study of other influencing factors.

2. Influence of the reaction time t and the pH

Fixing the reaction temperature at 95 ℃, changing the reaction time t and the pH value, respectively extracting the alcohol processing waste liquid, and calculating the corresponding extraction efficiency to obtain data mapping. The results are shown in FIG. 2.

Fig. 2 shows the effect of the reaction time t and pH on the extraction efficiency (curves from top to bottom are pH 1, pH 2 and pH 3). As can be seen from FIG. 2, the extraction efficiency eta increases with the increase of the time t, the increase trend is obvious before 8h, and the trend is gentle after 8 h; the smaller the pH, the higher the extraction efficiency.

3. Effect of extraction reagents

The extraction reagent is a key influence factor for extracting organic matters and increasing the comprehensive utilization rate of the alcohol processing waste liquid. Other reaction conditions were fixed here: extracting the alcohol processing waste liquid respectively with pH of 1, time T of 8h, temperature T of 95 ℃, sulfuric acid as reagent 1, alpha-protease as reagent 2 and mixture of sulfuric acid and alpha-protease as reagent 3, and calculating corresponding extraction efficiency to obtain data mapping. The results are shown in FIG. 3.

FIG. 3 is a graph showing the effect of extraction reagents on extraction efficiency eta. As can be seen from fig. 3, the extraction efficiency of sulfuric acid was the highest in reagent 1.

From the above experiments, the optimal extraction conditions were as follows: the extraction reagent is sulfuric acid, the pH value is 1, the time T is 8h, and the temperature T is 95 ℃. That is, embodiment 1 is the most preferable embodiment.

Second, total organic carbon content determination by total organic carbon analyzer

The total organic carbon content was measured using a total organic carbon analyzer (TOC) from the alcohol processing waste liquid (shown in fig. 4) of example 1 and the organic carbon nutrient (shown in fig. 5) obtained in example 1, respectively. The result shows that the total organic carbon content of the organic carbon nutrient prepared in the example 1 can reach 4.1 percent, and the basic requirement of the organic carbon fertilizer (the organic carbon content is 2 to 50 percent) can be met.

Third, fertilizer efficiency test

1. Preparation of potted plant test

Selecting two economic crops, namely Chinese cabbage and small tomato, suitable for the current season, setting 7 treatments in total by adopting a random block experimental design, repeating each treatment for 3 times, and simultaneously setting a blank test. The 7 test treatments included a blank test, conventional fertilization, example 1 alcohol process effluent, example 1 organic carbon nutrient + conventional fertilization mix, and 2 commercial liquid fertilizers. Formulating a pot experiment scheme, and carrying out soil treatment, planting of pakchoi and transplanting of tomato seedlings; and (5) calculating the fertilizing amount, culturing, and performing data acquisition and recording.

2. Design of pot culture experiment

And (3) fertilizing for 1 time per week according to a fertilization scheme on the premise of ensuring consistent soil humidity and illumination conditions after seedlings of the pakchoi grow and long leaves and small tomatoes are stably transplanted. The design fertilization protocol is shown in table 1 according to conventional fertilization metering.

TABLE 1 potted plant test fertilization protocol

3. Chinese cabbage potting test

(1) Potted pakchoi were photographed before each parameter was tested. The results are shown in FIG. 6.

FIG. 6 is a pre-test graph of a potted test pakchoi (1-7 groups from left to right). As can be seen from FIG. 6, the best growth was observed by the naked eye in group 4 (i.e., with the organic carbon nutrient of example 1).

(2) The measured data, including fresh weight, dry weight and leaf length, were compared for each test group. The results are shown in FIGS. 7-9.

Fig. 7 is the fresh weight data of the pakchoi of each test group of the potting test, fig. 8 is the fresh weight data of the pakchoi of each test group of the potting test, and fig. 9 is the leaf length data of the pakchoi of each test group of the potting test. As can be seen from FIGS. 7-9, the average fresh weight, dry weight and leaf length of each group of pakchoi change in a substantially consistent manner. Among them, the fresh weight, dry weight and leaf length levels of the pakchoi of group 4 were the greatest, leading to the same conclusion as before, that the pakchoi applied with the organic carbon nutrient of example 1 grew the best.

Specific analysis: first, compared with the indexes of the pakchoi with the alcohol processing waste liquid of the third group, the fresh weight of the pakchoi of the 4 th group is increased by 86 percent, and the dry weight of the pakchoi is increased by 100 percent, which shows that although the total organic carbon level is not obviously increased, specific components are possibly changed, the increase of water-soluble micromolecule organic matters causes that the nutrition is more easily absorbed by plants, and the fertilizer efficiency is obviously improved. Secondly, compared with the organic carbon nutrient and the conventional fertilizer in the 5 th group of the example 1, the indexes of the 4 th group of the pakchoi are increased by 10-48 percent, which shows that the using effect of the pakchoi mixed with the conventional fertilizer is not improved, certain inhibiting effect is generated between the pakchoi and the conventional fertilizer, and the mechanism of the pakchoi is to be deeply researched. Finally, the fertilizer efficiency of the group 4 is superior to that of two commercial liquid organic fertilizers, which shows that the product has better effect under the same concentration application condition, and proves that the product also has more excellent commercial value.

4. Field test of pakchoi

Only small-scale field trials under group 4 and group 1 (blank) conditions were performed, fertilizing 2 times, subject to the conditions. The test patterns are shown in FIGS. 10 and 11, and the comparative data are shown in Table 2.

TABLE 2 Chinese cabbage field test comparison data

Group of	Fresh weight/g	Dry weight/g	Leaf length/cm	SPAD
					1	405.0	28.1	23.9	32.3
4	601.6	32.2	26.8	36.0

Fig. 10 is a diagram before the test of the field test of the 1 st group of pakchoi, and fig. 11 is a diagram for testing the leaf length of the field test of the 1 st group and the 4 th group of pakchoi. As can be seen from fig. 10 and table 3, after the organic carbon nutrient of example 1 was applied, the fresh weight of pakchoi was increased by 48.5%, the dry weight was increased by 14.2%, the leaf length was increased by 12.1%, and the chlorophyll level was also better.

The above experiments show that the organic carbon nutrient of example 1 has significant fertilizer effect.

5. Tomato pot experiment

The fertilization scheme of the small tomatoes is the same as that of the small cabbages. The plant height H, column diameter D, SPAD-u, SPAD-m, SPAD-d, fresh weight on the ground, dry weight on the ground and yield were respectively tested, and the results are shown in FIGS. 12-19.

Fig. 12 is plant height H data of the small tomatoes of each test group of the potting test, fig. 13 is column diameter D data of the small tomatoes of each test group of the potting test, fig. 14 is SPAD-u data of the small tomatoes of each test group of the potting test, fig. 15 is SPAD-m data of the small tomatoes of each test group of the potting test, fig. 16 is SPAD-D data of the small tomatoes of each test group of the potting test, fig. 17 is above-ground fresh weight data of the small tomatoes of each test group of the potting test, fig. 18 is above-ground dry weight data of the small tomatoes of each test group of the potting test, and fig. 19 is yield data of the small tomatoes of each test group of the potting test.

As can be seen from FIGS. 12 to 19, the influence of each group on the plant height H of the fertilizer application is higher than that of the group 1 and the group 7, and the difference is obvious; the influence result of each group of fertilization on the column diameter D is that the 6 th group and the 7 th group have the best performance, are higher than the 1 st group, and have obvious difference; the influence of each group of fertilizer on chlorophyll is not obvious. However, from the fresh weight, dry weight and yield per pot of tomatoes, the treatment group 5 with the organic carbon nutrient + conventional fertilization mix of example 1 was significantly higher than the other treatments and had reached a level of differential significance, and the treatment group 4 with the organic carbon nutrient of example 1 was also significantly better than the first three treatments, but had no significant difference from the two commercial liquid fertilizer treatments.

Therefore, the organic carbon nutrient in the embodiment 1 and the conventional fertilization mixture can obviously promote the growth of tomatoes and improve the yield, and the treatment of the organic carbon nutrient and the conventional fertilization mixture is obviously better than that of the liquid fertilizer sold in the market, so that the organic carbon nutrient and the conventional fertilization mixture have wide development and application prospects.

The research results show that the extraction efficiency of the organic carbon nutrient prepared by extracting organic matters from the alcohol processing waste liquid can reach 2.3 times, and the total organic carbon content of the organic carbon nutrient after extraction can reach 4.1 percent; plant nutrition test results also show that the organic carbon nutrient prepared from the alcohol processing waste liquid has practical application and popularization values.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an organic carbon nutrient by using alcohol processing waste liquid is characterized by comprising the following steps:

(3) adding an acid-base blender into the solution B to obtain a solution C;

2. The method for preparing organic carbon nutrient by using alcohol processing waste liquid according to claim 1, wherein in the step (1), the acid indicator is at least one of sulfuric acid, nitric acid and phosphoric acid; the pH value of the acidic regulator added into the alcohol processing waste liquid is 1-2.

3. The method for preparing organic carbon nutrient from alcohol processing waste liquid as claimed in claim 1, wherein in step (1), the temperature of the heating and stirring is 90-95 ℃, the rotation speed is 100-.

4. The method for preparing organic carbon nutrient from alcohol processing waste liquid according to claim 1 or 3, wherein in the step (1), the temperature of the heating and stirring is 95 ℃, the rotating speed is 180r/min, and the time is 8 h.

5. The method for preparing an organic carbon nutrient from an alcohol processing waste liquid according to claim 1, wherein in the step (2), the macroelement is at least one of urea, potassium nitrate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium sulfate.

6. The method for preparing an organic carbon nutrient from alcohol processing waste liquid according to claim 1, wherein in the step (2), the secondary element is chelated calcium EDCA-10 and/or magnesium sulfate.

7. The method for preparing an organic carbon nutrient from an alcohol processing waste liquid according to claim 1, wherein in the step (2), the trace element is at least one of chelated iron, boric acid, chelated manganese, chelated copper, chelated zinc, chelated molybdenum and chelated cobalt.

8. The method for preparing an organic carbon nutritional agent according to claim 1, wherein in the step (3), the acid-base blending agent is added to the solution B at a pH value of 5-8.

9. The method for preparing organic carbon nutrient from alcohol processing waste liquid according to claim 1, wherein in the step (4), the concentration is carried out until the total organic carbon content in the solution C is 2% -12%.

10. The method for preparing organic carbon nutrient from alcohol processing waste liquid according to claim 1, wherein in the step (4), the microwave radiation has a power of 2-6kW and a time of 2-4 h.