阅读说明：本技术 一种以过酸化沼液为主要原料的青贮添加剂及其制备方法与应用 (Silage additive taking peracid biogas slurry as main raw material and preparation method and application thereof ) 是由 付龙云 王艳芹 李彦 赵自超 田叶 仲子文 于 2019-11-12 设计创作，主要内容包括：本发明涉及一种以过酸化沼液为主要原料的青贮添加剂及其制备方法与应用。包括如下重量份的组分：过酸化沼液10份,自来水10～20份,果胶酶0.04～0.06份,木聚糖酶0.04～0.06份,过氧化氢酶0.01～0.03份。本发明以厌氧沼气发酵失败产生的过酸化沼液为主要原料,经曝气、紫外线照射等处理步骤,加入果胶酶、木聚糖酶和过氧化氢酶等酶类制得青贮添加剂。本发明充分利用过酸化沼液中富含的丙酸、乙酸,在牧草、作物秸秆的青贮中具有良好的作用,制备工艺简洁、产品成本低廉、效果突出,在农业废弃物循环利用领域应用前景广阔。(The invention relates to an ensiling additive taking peracid biogas slurry as a main raw material, and a preparation method and application thereof. Comprises the following components in parts by weight: 10 parts of over-acidified biogas slurry, 10-20 parts of tap water, 0.04-0.06 part of pectinase, 0.04-0.06 part of xylanase and 0.01-0.03 part of catalase. The invention takes peracid biogas slurry generated by anaerobic biogas fermentation failure as a main raw material, and enzymes such as pectinase, xylanase, catalase and the like are added to prepare the silage additive through the treatment steps of aeration, ultraviolet irradiation and the like. The invention fully utilizes the propionic acid and the acetic acid which are rich in the peracid biogas slurry, has good effect in the ensiling of pasture and crop straws, has simple preparation process, low product cost and prominent effect, and has wide application prospect in the field of recycling of agricultural wastes.)

1. An ensiling additive taking peracid biogas slurry as a main raw material is characterized by comprising the following components in parts by weight:

10 parts of over-acidified biogas slurry, 10-20 parts of tap water, 0.04-0.06 part of pectinase, 0.04-0.06 part of xylanase and 0.01-0.03 part of catalase;

the enzyme activity of the pectinase is 3.0 multiplied by 10³～7.0×10³IU/g；

The enzyme activity of the xylanase is 0.5 multiplied by 10⁴～1.5×10⁴IU/g；

The enzyme activity of the catalase is 0.5 multiplied by 10⁴～1.5×10⁴IU/g。

2. The silage additive of claim 1, wherein the over-acidified biogas slurry is a liquid obtained by removing biogas residues from a coarse liquid of the over-acidified biogas slurry discharged after anaerobic biogas fermentation of vegetable waste or/and kitchen waste fails, and the pH value is 4.0-5.5.

3. The silage additive of claim 1, wherein the pectinase has an enzyme activity of 5.0 x 10³IU/g, enzyme activity of xylanase is 1.0 x 10⁴IU/g, enzyme activity of catalase is 1.0X 10⁴IU/g。

4. The silage additive of claim 1, comprising the following components in parts by weight: 10 parts of over-acidified biogas slurry, 10 parts of tap water, 0.05 part of pectinase, 0.05 part of xylanase and 0.02 part of catalase.

5. The method for preparing the silage additive taking the peracid biogas slurry as the main raw material as claimed in claim 1, is characterized by comprising the following steps:

(1) aerating the peracid biogas slurry to prepare a treatment solution 1;

(2) treating the treatment solution 1 prepared in the step (1) by ultraviolet irradiation, wherein methanogenic bacteria in the biogas slurry after the ultraviolet treatment are not detected, and escherichia coli is reduced to below the detection limit of 3cfu/mL to prepare a treatment solution 2;

(3) taking the treatment liquid 2 prepared in the step (2) according to the parts by weight, and adding water in corresponding parts by weight to mix uniformly to prepare a diluent;

(4) and (4) adding pectinase, xylanase and catalase in corresponding parts by weight into the diluent prepared in the step (3), and uniformly mixing to obtain the silage additive.

6. The preparation method of the silage additive as claimed in claim 5, wherein the peracid biogas slurry in step (1) is a liquid obtained by centrifuging a crude peracid biogas slurry at 2000-5000 rpm for 5-20 min at room temperature to remove biogas residues;

preferably, the centrifugation conditions are: centrifuge at 3000rpm for 10 min.

7. The method for preparing an ensiling additive according to claim 5, wherein the aeration conditions of the step (1): the treatment time is 12-36 h, and the aeration ventilation volume is 2.0-4.0 m³/h；

Preferably, the aeration time of the step (1) is 18h, and the aeration volume is 3.0m³/h。

8. The method for preparing silage additive according to claim 5, wherein the ultraviolet irradiation treatment in step (2) is ultraviolet lamp irradiation, and the ultraviolet output dose is 200-400 μ W/cm²Continuously irradiating for 60-120 min;

preferably, the ultraviolet lamp tube irradiates, and the ultraviolet output dose is 300 mu W/cm²The irradiation was continued for 90 min.

9. The method for preparing the silage additive as claimed in claim 5, wherein the concentration of the propionic acid and the concentration of the acetic acid in the diluent prepared in the step (3) are 1000-1800 mg/L and 1600-3600 mg/L respectively;

preferably, the concentration of the propionic acid in the diluent prepared in the step (3) is 1500mg/L, and the concentration of the acetic acid in the diluent is 3000 mg/L.

10. The method of using the silage additive of claim 1, comprising the steps of:

a. smashing the silage raw material into fragments with the length of 1.0-3.0 cm, and removing impurities;

b. mixing silage raw materials and silage additives according to a mass ratio of 20: (1-3), uniformly mixing, subpackaging, compacting and sealing;

c. ensiling and storing for 20-40 days at room temperature to obtain ensiling feed;

preferably, the mass ratio of the silage raw materials to the silage additives in the step b is 9: 1;

preferably, the ensiling is stored for 30d in step c.

The technical field is as follows:

the invention relates to an ensiling additive taking peracid biogas slurry as a main raw material, and a preparation method and application thereof, and belongs to the technical fields of agricultural biotechnology and rural environmental protection.

Background art:

with the rapid development of livestock breeding industry in China, the market demand for various coarse and fine feeds is increasingly expanded. In the breeding of herbivorous animals such as cattle and sheep, coarse fodder such as pasture and straw plays an important role. However, due to the influence of factors such as seasons, the supply of fresh pasture and straw feed is lacked in most of the areas in China in winter and spring, the pasture and the straw feed can be replaced by the dry pasture and the dry straw, and indexes such as nutrition, flavor, palatability and the like of the feed are greatly reduced. Ensiling is a long-standing and very effective way for preserving fresh plant materials, and the traditional ensiling is not added with other components, only pasture and the like are bundled, compacted and stored in a sealing way, and the effect of preservation can be achieved by generating lactic acid through anaerobic metabolism of indigenous lactic acid bacteria. However, the traditional silage has the inherent defects of poor stability, large regional difference, high dry matter loss rate and the like, is not completely suitable for modern intensive production modes, and artificially adding silage additives such as microbial agents, organic acids, biological enzymes and the like is an effective mode for solving the problem. A plurality of studies at home and abroad show that the addition of organic acids such as propionic acid, acetic acid and the like into the ensilaged materials can quickly reduce the pH value of the environment, inhibit the growth of aerobic putrefying bacteria, effectively prevent mildewing and deterioration and better preserve the nutritive value of the materials. Especially, the addition of the organic acid additive takes effect more quickly and the preservation of dry matters is better in view of that the physiological metabolism of the viable bacteria agent consumes a part of nutrient substances, so that the application of the viable bacteria agent in large-scale silage is more suitable. How to obtain cheap organic acid resources is very important for reducing ensiling cost and realizing resource recycling.

Anaerobic biogas fermentation is a common technical mode in the process of treating agricultural wastes, and the technology can not only obtain high-quality renewable energy source biogas, but also obtain biogas residues and biogas slurry as excellent organic fertilizers, and is rapidly developed in China in recent years. However, it is worth noting that the anaerobic biogas fermentation process needs to be accurately regulated and controlled to ensure the normal production of biogas, and factors such as excessive organic load, inappropriate carbon-nitrogen ratio, acid-base imbalance and the like may cause poor fermentation and even failure of biogas production. When materials such as vegetable wastes, kitchen waste and the like which are rich in water and carbohydrate are subjected to anaerobic fermentation, organic acid is generated very quickly due to vigorous microbial catabolism, and if excessive accumulation occurs due to the fact that the organic acid cannot be decomposed in time, the biogas slurry is over-acidified, so that the pH and the pH value of the environment far exceed the tolerance capability of methanogens, and the fermentation system is collapsed. Although the fermentation system after collapse can try to recover by adding alkaline substances, reducing organic load and other ways, generally, the biogas slurry after fermentation failure can only be discharged and discarded, and an effective utilization way is lacked, so that the waste of resources is caused. Compared with the normally fermented biogas slurry, the over-acidified biogas slurry contains more abundant organic acids such as propionic acid, acetic acid and the like, and can be used as a cheap and high-quality silage additive if reasonably treated to remove residual methanogens and supplement other substances beneficial to silage.

Chinese patent document CN110338282A (application number: 201910743301.6) discloses a compound additive for preparing high-moisture silage, a preparation method and application thereof, and the compound additive comprises the following raw materials in parts by weight: 250 portions of formic acid 200-. However, the composite additive adopts industrial raw materials, so that the cost is high, and pollution caused by impure raw materials exists in the actual use and finally the meat quality of livestock is influenced.

The invention content is as follows:

aiming at the defects of the prior art, the invention provides an ensiling additive taking peracid biogas slurry as a main raw material, and a preparation method and application thereof.

The silage additive provided by the invention is prepared by using peracid biogas slurry in anaerobic biogas fermentation as a main raw material, is rich in organic acids such as propionic acid and acetic acid required by silage and ammonium compounds with a certain concentration, further removes methanogens and pathogenic microorganisms through processes such as aeration and ultraviolet irradiation, and supplements biological enzymes beneficial to the silage process. The ensiling additive is obtained, so that high-value utilization of anaerobic fermentation peracid biogas slurry is realized, and waste is changed into wealth; the method is applied to the ensiling process of plant materials such as straw, vegetable waste and the like, can effectively inhibit harmful microorganisms such as mould, escherichia coli and the like, promotes the growth and the propagation of lactic acid bacteria and the generation of lactic acid, accelerates the ensiling conversion process and improves the ensiling quality.

Description of terms:

anaerobic biogas fermentation: under the anaerobic condition, various organic matters undergo the complex microbial metabolic activities mainly including macromolecular catabolism, organic acid generation and methane generation to finally generate CH₄And CO₂Mainly the process of marsh gas, which is completed by complex microbial communities including clostridium, bacteroides, methanogen and the like.

Over-acidification biogas slurry crude liquid: when materials with high water content and abundant carbohydrates such as vegetable wastes and kitchen wastes are used as substrates for anaerobic biogas fermentation, if the process is controlled improperly, the phenomena of excessive accumulation of organic acids and fermentation failure occur due to too fast microbial catabolism, the biogas slurry contains a large amount of organic acids such as propionic acid and acetic acid, the pH is lower than 5.5 (the physiological limit of normal survival of most methanogens), and the biogas slurry is called peracid biogas slurry crude liquid.

Ensiling: fresh plant materials are compacted and then are placed in a closed space isolated from air for long-term storage, lactic acid is generated through the anaerobic fermentation of microorganisms such as indigenous lactic acid bacteria of the plants or organic acid, microbial inoculum and the like are artificially added to inhibit the growth of harmful microorganisms, so that the lignification process of the plant materials can be greatly slowed down, the loss of nutrients such as saccharides and proteins is reduced, and special flavor is given to the plant materials. Ensiling is a common means of processing herbivorous livestock feed.

Silage additives: in practical production, in order to achieve different purposes of shortening silage time, endowing silage with special flavor, improving palatability and the like, different additives are often additionally added in the silage process, and are divided into living microorganisms such as lactic acid bacteria and the like, organic acids such as propionic acid and acetic acid, alkalis such as ammonia water and ammonium bicarbonate and different types of biological enzymes such as cellulase and xylanase and the like, and the substances are collectively called silage additives.

The technical scheme of the invention is as follows:

the silage additive taking peracid biogas slurry as a main raw material comprises the following raw material components in parts by weight:

10 parts of over-acidified biogas slurry, 10-20 parts of tap water, 0.04-0.06 part of pectinase, 0.04-0.06 part of xylanase and 0.01-0.03 part of catalase;

the enzyme activity of the pectinase is 3.0 multiplied by 10³～7.0×10³IU/g；

The enzyme activity of the xylanase is 0.5 multiplied by 10⁴～1.5×10⁴IU/g；

The enzyme activity of the catalase is 0.5 multiplied by 10⁴～1.5×10⁴IU/g。

According to the invention, the peracid biogas slurry is liquid obtained by removing biogas residues from a crude peracid biogas slurry discharged after anaerobic biogas fermentation failure of vegetable waste or/and kitchen waste, and the pH value is 4.0-5.5.

The pectinase, xylanase and catalase are all commercial enzymes.

Preferably, the enzyme activity of the pectinase is 5.0 x 10³IU/g, enzyme activity of xylanase is 1.0 x 10⁴IU/g, enzyme activity of catalase is 1.0X 10⁴IU/g。

According to the invention, the silage additive comprises the following raw material components in parts by weight: 10 parts of over-acidified biogas slurry, 10 parts of tap water, 0.05 part of pectinase, 0.05 part of xylanase and 0.02 part of catalase.

The preparation method of the silage additive taking the peracid biogas slurry as the main raw material comprises the following steps:

(1) aerating the peracid biogas slurry to prepare a treatment solution 1;

(2) treating the treatment solution 1 prepared in the step (1) by ultraviolet irradiation, wherein methanogenic bacteria in the biogas slurry after the ultraviolet treatment are not detected, and escherichia coli is reduced to below the detection limit of 3cfu/mL to prepare a treatment solution 2;

(3) taking the treatment liquid 2 prepared in the step (2) according to the parts by weight, and adding water in corresponding parts by weight to mix uniformly to prepare a diluent;

(4) and (4) adding pectinase, xylanase and catalase in corresponding parts by weight into the diluent prepared in the step (3), and uniformly mixing to obtain the silage additive.

Because methanogens are very sensitive to oxygen, the methanogens in the biogas slurry lose activity through aeration, and meanwhile, the aeration also plays a certain role in reducing the ammonia concentration in the biogas slurry, so the methanogens can be inactivated and the ammonia concentration can be reduced through aeration; ultraviolet radiation further kills methanogens and pathogenic microorganisms.

According to the invention, the peracid biogas slurry in the step (1) is a liquid obtained by centrifuging a crude peracid biogas slurry at 2000-5000 rpm for 5-20 min at room temperature to remove biogas residues.

Further preferably, the centrifugation conditions are: centrifuge at 3000rpm for 10 min.

According to the invention, the aeration conditions of the step (1) are preferably as follows: the treatment time is 12-36 h, and the aeration ventilation volume is 2.0-4.0 m³/h。

Further preferably, the aeration conditions of the step (1): the treatment time is 18h, and the aeration ventilation is 3.0m³/h。

According to the invention, the ultraviolet irradiation treatment in the step (2) is preferably ultraviolet lamp irradiation, and the ultraviolet output dose is 200-400 muW/cm²Continuously irradiating for 60-120 min.

Further preferably, the ultraviolet lamp tube irradiates, and the ultraviolet output dose is 300 mu W/cm²The irradiation was continued for 90 min.

According to the preferable selection of the invention, the concentration of the propionic acid in the diluent prepared in the step (3) is 1000-1800 mg/L, and the concentration of the acetic acid is 1600-3600 mg/L.

More preferably, the concentration of the propionic acid in the diluent prepared in the step (3) is 1500mg/L, and the concentration of the acetic acid in the diluent is 3000 mg/L.

The application method of the silage additive taking the peracid biogas slurry as the main raw material comprises the following steps:

a. smashing the silage raw material into fragments with the length of 1.0-3.0 cm, and removing impurities;

b. mixing silage raw materials and silage additives according to a mass ratio of 20: (1-3), uniformly mixing, subpackaging, compacting and sealing;

c. and (5) ensiling and storing for 20-40 days at room temperature to obtain the ensiling feed.

According to the invention, the mass ratio of the silage raw materials to the silage additives in the step b is 9: 1.

preferably, according to the invention, the silage is stored for 30d in step c.

The invention has the following function principle:

in the anaerobic biogas fermentation process, excessive accumulation of organic acid, rapid decrease of pH, over-acidification of a system, failure of fermentation biogas production caused by exceeding the bearing range of a biogas fermentation microbial flora, often caused by excessive organic load, improper carbon-nitrogen ratio, acid-base imbalance and the like, and the original biogas slurry is usually and completely discharged for faster recovery of normal biogas production, wherein the over-acidified biogas slurry is still lack of an effective utilization method at present. The peracid biogas slurry is rich in organic acids such as propionic acid and acetic acid, and the propionic acid and the acetic acid can play an important role in ensiling of pasture and straws. Therefore, the composite silage additive based on the peracid biogas slurry is obtained by adopting the processes of centrifugation, aeration, ultraviolet disinfection and the like, adjusting the concentration of the organic acid to a proper level, and supplementing pectinase, xylanase and catalase capable of degrading pectin and hemicellulose and removing oxygen free radicals. The silage additive has low cost and obvious effect, and can play a good role in the silage of plant materials such as pasture, straws and the like.

The invention has the following beneficial effects:

1. the ensiling effect is good. The silage additive disclosed by the invention contains organic acids such as propionic acid and acetic acid, the pH value of plant materials can be quickly reduced, and the growth of harmful microorganisms such as mould and escherichia coli can be effectively inhibited. The silage also contains compound enzymes consisting of pectinase, xylanase and catalase, can primarily decompose pectin and hemicellulose which are difficult to degrade in plant materials, improves the palatability and digestibility of silage, and simultaneously can remove oxygen free radicals in the environment by the catalase, reduce the oxidation-reduction potential and reduce the oxidation loss of the plant materials;

2. the cost is low. The silage additive is based on peracid biogas slurry generated by anaerobic biogas fermentation failure, propionic acid and acetic acid do not need to be purchased additionally, and waste materials can be changed into valuable materials and agricultural resources can be fully utilized;

3. the safety is good. The main component of the silage additive, namely the peracid biogas slurry, comes from anaerobic biogas fermentation, the anaerobic biogas fermentation process can inhibit the growth and the propagation of most aerobic pathogenic microorganisms, and the aeration and ultraviolet sterilization processes are assisted to remove methanogens and residual pathogenic bacteria, so that the biological safety risk of the silage process is avoided;

4. the preparation process is simple. The preparation method of the silage additive prepared by the invention is simple, the adopted technologies are common technologies in the technical fields of environmental engineering and microorganisms, and the used equipment is common environment and microorganism fermentation equipment, so that the silage additive is easy to popularize;

5. the environmental protection benefit is outstanding. The method can solve the problem of treatment of peracid biogas slurry generated by anaerobic biogas fermentation failure, realizes cyclic utilization of resources, does not add heavy metal elements and refractory components in the preparation process of the additive, and does not cause secondary pollution.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not specifically illustrated and are in accordance with the prior art in the field.