阅读说明：本技术 一种生物质废弃物的综合处理与资源化利用方法 (Comprehensive treatment and resource utilization method of biomass waste ) 是由 章磊 陈秀 陈建 戴世良 何先标 徐旭明 程燕 于 2021-09-16 设计创作，主要内容包括：本发明涉及固废和废水的无害化处置及资源化利用领域,旨在提供一种生物质废弃物的综合处理与资源化利用方法。包括：将羽毛、亚硫酸钠和水产养殖废水进行混合后水解磺化,将水解磺化液、畜禽粪便、煤、水产养殖废水加入棒磨机中,采用湿磨工艺处理得到多元浆料；将多元浆料与压缩纯氧喷入水煤浆气化炉中,进行气化和熔融处理,得到气态产物和液态熔渣；进行激冷分离,得到含有CO和H-(2)的混合气体,其余有害元素被固定在玻璃态渣中排出。本发明能同时解决多种生物质废弃物的排放难题,在消纳了大量养殖业生物质废弃物的同时,还节省了多元浆料制备的煤原料、制浆用水、水煤浆添加剂,全方位降低了制浆成本,具有显著的环保效益和经济效益。(The invention relates to the field of harmless treatment and resource utilization of solid waste and wastewater, and aims to provide a comprehensive treatment and resource utilization method of biomass waste. The method comprises the following steps: mixing feather, sodium sulfite and aquaculture wastewater, then carrying out hydrolysis sulfonation, adding hydrolysis sulfonated liquid, livestock and poultry manure, coal and aquaculture wastewater into a rod mill, and carrying out wet milling process treatment to obtain multi-element slurry; spraying the multi-element slurry and compressed pure oxygen into a coal water slurry gasification furnace, and carrying out gasification and melting treatment to obtain a gaseous product and liquid molten slag; chilling and separating to obtain the product containing CO and H 2 The rest harmful elements are fixed in the glassy state slag and discharged. The invention can simultaneously solve the difficult problem of discharging various biomass wastes, saves coal raw materials, water for pulping and coal water slurry additives prepared by multi-element slurry while consuming a large amount of biomass wastes in the breeding industry, reduces the pulping cost in all directions,has obvious environmental protection benefit and economic benefit.)

1. A comprehensive treatment and resource utilization method of biomass waste is characterized by comprising the following steps:

(1) mixing the feathers, sodium sulfite and aquaculture wastewater according to the mass ratio of 30: 10: 60, and then hydrolyzing and sulfonating for 6 hours at 80 ℃ under the stirring condition to obtain a hydrolyzed sulfonated liquid;

(2) adding the hydrolyzed sulfonated liquid, the livestock and poultry manure, the coal and the aquaculture wastewater into a rod mill according to the mass ratio of 1: 5-9: 55: 35-39, and carrying out wet milling treatment to obtain a multi-element slurry;

(3) spraying the multi-element slurry and compressed pure oxygen into a coal water slurry gasification furnace according to the mass ratio of 2: 1, and carrying out gasification and melting treatment to obtain a gaseous product and liquid slag;

(4) chilling and separating the gaseous product and the liquid slag to obtain the product containing CO and H₂The rest harmful elements are fixed in the glassy state slag and discharged.

2. The method of claim 1, wherein the feathers are any one of chicken, duck or goose feathers.

3. The method as claimed in claim 1, wherein the livestock manure is any one of manure from broiler, pig and dairy farms.

4. The method of claim 1, wherein the aquaculture wastewater is from various aquaculture farms to replace industrial clean water required for pulping.

5. The method of claim 1, wherein the conditions of the wet milling process are: the rotation speed is 20rpm, and the viscosity of the mixture obtained after wet grinding is 1500 mPas or less.

6. The method according to claim 1, wherein the reaction temperature in the coal water slurry gasification furnace is 1100-1500 ℃ and the pressure is 0.5-6.5 MPa.

Technical Field

The invention belongs to the field of harmless treatment and resource utilization of solid waste and wastewater, and particularly relates to a comprehensive treatment and resource utilization method of biomass waste.

Background

The requirement of people on the quality of life is continuously improved, the scale of the breeding industry in China is enlarged year by year, and a large amount of biomass waste such as livestock and poultry breeding waste and aquaculture waste water is generated, so that the agriculture industry is the largest non-point source pollution industry in China. The resource utilization of biomass waste is the most effective way for pollution control in the breeding industry, the comprehensive utilization ratio of livestock and poultry breeding waste (the water content is usually 60-80%) in China is not high, one fourth of the livestock and poultry breeding waste is not effectively treated and utilized, most aquaculture waste water (the pH is usually 7.0-8.5) is directly discharged into a water body environment, and the resource utilization space of the biomass waste in the breeding industry in China is huge.

At present, one important direction of the resource utilization of the biomass waste in the breeding industry is planting and breeding cycle, the livestock and poultry breeding waste is converted into organic fertilizer or compound fertilizer by direct returning, composting fermentation and other modes, the combination of fertilizer utilization and planting and breeding is realized, and the aquaculture waste water can be used for crop irrigation. However, the composting time period is long, the reduction is difficult to complete, the occupied area is large, the fertility of the organic fertilizer is poor, various heavy metals are easy to enrich, malodorous gas can be generated in the composting process, and certain environmental and health risks exist. With the continuous separation of the breeding industry and the planting industry in China, the planting and breeding combination is not tight any more, and the biomass wastes which can be used by planting and breeding circulation are very limited. Energy resource is another important direction for the utilization of biomass waste in the breeding industry, and the biogas engineering construction is once implemented in China and rural areas by taking families as units, and the livestock and poultry breeding waste is subjected to anaerobic digestion treatment to produce biogas energy. However, stable raw material supply and strict temperature and humidity control are required in the anaerobic digestion process, the methane tank facilities need manual maintenance, and secondary pollution is easily caused by difficultly treated methane slag and methane liquid, so that the further wide application of the energy resource technology for anaerobically digesting the biomass waste is limited.

In summary, the utilization of biomass waste in the breeding industry mainly comprises two directions of planting and breeding cycle and energy resource, but still has the following problems: (1) the composting time period is long, the decrement is not thorough, the fertility of the organic fertilizer is poor, and the heavy metal enrichment and malodorous gas can cause environmental and health risks; (2) the planting and breeding separation phenomenon is obvious, and the digestion capacity of planting and breeding circulation on the biomass waste in the breeding industry is seriously insufficient; (3) anaerobic digestion requires stable raw material supply and strict temperature and humidity control, and the difficultly treated biogas residues and biogas slurry are easy to cause secondary pollution. Therefore, the development of a new method for comprehensive treatment and resource utilization of biomass waste has good practical significance.

Disclosure of Invention

The invention aims to solve the technical problems of overcoming the defects in the prior art, providing a method for comprehensively utilizing biomass waste and solving the problems of reduction, harmlessness and resource utilization of the biomass waste in the breeding industry.

In order to solve the technical problem, the solution of the invention is as follows:

the comprehensive treatment and resource utilization method of the biomass waste comprises the following steps:

(1) mixing the feathers, sodium sulfite and aquaculture wastewater according to the mass ratio of 30: 10: 60, and then hydrolyzing and sulfonating for 6 hours at 80 ℃ under the stirring condition to obtain a hydrolyzed sulfonated liquid;

(2) adding the hydrolyzed sulfonated liquid, the livestock and poultry manure, the coal and the aquaculture wastewater into a rod mill according to the mass ratio of 1: 5-9: 55: 35-39, and carrying out wet milling treatment to obtain a multi-element slurry;

(3) and spraying the multi-element slurry and the compressed pure oxygen into a coal water slurry gasification furnace according to the mass ratio of 2: 1, and carrying out gasification and melting treatment to obtain a gaseous product and liquid slag.

(4) Chilling and separating the gaseous product and the liquid slag to obtainContaining CO and H₂The rest harmful elements are fixed in the glassy state slag and discharged.

As a preferable scheme of the invention, the feather is any one of chicken feather, duck feather and goose feather.

In a preferred embodiment of the present invention, the livestock manure is any one of manure from a broiler house, a pig house, and a dairy farm.

As a preferable scheme of the invention, the aquaculture wastewater comes from various aquaculture farms and is used for replacing industrial clean water required by pulping.

As a preferred embodiment of the present invention, the wet milling process conditions are: the rotation speed is 20rpm, and the viscosity of the mixture obtained after wet grinding is 1500 mPas or less.

As a preferable scheme of the invention, the reaction temperature in the coal water slurry gasification furnace is 1100-1500 ℃, and the pressure is 0.5-6.5 MPa.

Description of the inventive principles:

the feather contains more than 80% of protein, a small amount of calcium, magnesium and potassium elements, and trace elements such as zinc, iron and the like. The feathers are stirred in the aquaculture wastewater at 80 ℃ added with sodium sulfite to carry out hydrolysis and sulfonation reaction under the high temperature condition, so as to obtain hydrolyzed sulfonated liquid to replace a coal water slurry additive, improve the slurrying characteristic of coal in the aquaculture wastewater in the wet milling and slurrying process, and reduce the slurrying cost. In addition, alkali metals, alkaline earth metals and partial transition metal elements such as sodium, calcium, iron, magnesium, potassium and the like which are left in the hydrolyzed sulfonated liquid by the feathers and the sodium sulfite can play an obvious catalytic role in the gasification reaction of the multi-element slurry, and promote the generation of effective synthesis gas.

The water content of the livestock and poultry manure is very high, and is usually 60-80%. The invention directly utilizes the livestock and poultry manure in the form of suspended matters without drying pretreatment, thereby greatly reducing the recycling cost of the livestock and poultry manure. The content of volatile components in the livestock manure is as high as 60-70%, which indicates that the combustion speed of the livestock manure is higher and the ignition point is low, the invention can improve the ignition performance of multi-element slurry by adding the livestock manure, and the content of O: c and H: the C ratio is obviously higher than that of coal, which indicates that the livestock manure is easy to volatilize and carry out energy conversion, and gasification and pyrolysis are easy to occur. The invention mixes the livestock and poultry manure to replace part of coal for gasification reaction to generate high value-added synthesis gas, can realize the recycling of the cultivation waste, and saves the coal cost.

The aquaculture wastewater contains main pollutants such as suspended particulate matters, organic matters, ammonia nitrogen, nitrite, phosphorus and the like, the suspended particulate matters mainly refer to residual baits, fish feces and the like, and the organic matters mainly comprise humus substances, carbohydrates, protein substances, aldehydes with low molecular weight and the like. The aquaculture wastewater is alkaline generally, the pH value is between 7.0 and 8.5, and the two main characteristics are low pollutant concentration and large single-time water discharge. According to the invention, the aquaculture wastewater is used as the water for pulping, so that a huge pollution source is converted into a process water source, the ecological damage caused by directly discharging the aquaculture wastewater into a water body environment is avoided, and the water cost of the coal water slurry gasification process is avoided. In addition, organic matters in the aquaculture wastewater are recycled in the process of gasification reaction of the multi-element slurry.

The invention utilizes feather to prepare hydrolytic sulfonated liquid to replace a coal water slurry additive, utilizes livestock and poultry manure to replace part of raw material coal, utilizes aquaculture wastewater to replace industrial clean water, jointly prepares a novel multi-element slurry fuel, gasifies and melts the slurry fuel in a coal water slurry gasification furnace to generate synthesis gas with high added value and glassy state slag fixed with harmful elements, and comprehensively reduces the pulping cost of the coal water slurry while harmlessly and resourcefully utilizing biomass wastes in the aquaculture industry.

Compared with the prior art, the invention has the technical advantages that:

(1) the invention develops a new resource utilization method for comprehensively treating various biomass wastes in the aquaculture industry aiming at the respective component characteristics of feathers, livestock and poultry manure and aquaculture wastewater, and solves the problem of discharge of various biomass wastes by using one technology.

(2) While a large amount of biomass waste of the aquaculture industry is consumed, the coal raw material, the water for pulping and the coal water slurry additive prepared by the multi-element slurry are saved, the pulping cost is reduced comprehensively, and the environment-friendly and economic benefits are remarkable.

(3) The pollutants in the biomass waste are subjected to high-temperature and high-pressure gasification melting reaction to realize resource utilization, are converted into synthesis gas with high added value and slag discharge for fixing harmful elements, and can be further utilized as chemical production raw materials and building materials.

(4) Based on the new method provided by the invention, the original high-investment low-income aquaculture biomass waste treatment technology can be combined with the production of high-added-value synthesis gas or chemical products, and the economic benefit of the biomass waste is greatly improved.

Drawings

Fig. 1 is a schematic flow chart of the comprehensive treatment and resource utilization method of biomass waste according to the present invention.

Reference numerals: 1, feather 1; 2, sodium sulfite 2; aquaculture wastewater 3; a heating and stirring device 4; 5 parts of livestock and poultry manure; 6 parts of coal; a rod mill 7; a gasification furnace 8; synthesis gas 9; a glassy slag 10.

Detailed Description

The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.

The invention utilizes feather to prepare hydrolytic sulfonated liquid to replace a water-coal-slurry additive, utilizes livestock and poultry manure to replace part of raw material coal, utilizes aquaculture wastewater to replace industrial cleaning water, jointly prepares novel multi-element slurry fuel, gasifies and melts the slurry fuel in a water-coal-slurry gasification furnace, and generates synthesis gas with high added value and glassy slag with fixed harmful elements. .

The specific flow is shown in figure 1. Adding the feather 1, sodium sulfite 2 and aquaculture wastewater 3 into a heating and stirring device 4 according to the mass ratio of 30: 10: 60, and heating and stirring for 6 hours at the temperature of 80 ℃; the feather 1 is subjected to hydrolysis sulfonation reaction in an alkaline environment to obtain hydrolysis sulfonation liquid with similar effect to the coal water slurry additive. Then, hydrolyzing the sulfonated liquid, aquaculture wastewater 3, livestock and poultry according to the mass ratio of 1: 5-9: 55: 35-39And adding the excrement 5 and the coal 6 into a rod mill 7, preparing and obtaining the multi-element slurry with the viscosity of less than 1500mPa & s by adopting a wet grinding process, and controlling the rotating speed to be 20prm during wet grinding. And finally, injecting the multi-component slurry and the compressed pure oxygen into a coal water slurry gasification furnace 8 from a nozzle together according to the mass ratio of 2: 1, and gasifying and melting at 1100-1500 ℃ and 0.5-6.5 MPa to obtain a gaseous product and liquid slag. Chilling and separating the gaseous product and the liquid slag to obtain CO and H with high added value₂The synthesis gas 9 is mainly, and harmful elements are fixed in the glassy slag 10 and discharged.

Example 1:

in the embodiment, the selected materials are Shenhua coal, chicken feather, chicken manure of a broiler chicken farm and eel farm culture wastewater.

Heating and stirring chicken feather, sodium sulfite and eel farm culture wastewater for 6 hours at the temperature of 80 ℃ to obtain chicken feather hydrolyzed sulfonated liquid, wherein the mass percentage of the chicken feather is 30 percent, and the mass percentage of the sodium sulfite is 10 percent. And preparing the chicken feather hydrolyzed sulfonated liquid, chicken manure in a broiler farm, coal and eel farm culture wastewater into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the chicken feather hydrolyzed sulfonated liquid to the chicken manure in the broiler farm to the coal to the eel farm culture wastewater is 1: 5: 55: 39. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1300 ℃ and 3.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Example 2:

the materials selected in the embodiment are Shenhua coal, duck feather, pig manure of a pig farm and breeding wastewater of a grass carp farm.

Heating and stirring the duck feather, sodium sulfite and the grass carp farm culture wastewater for 6 hours at the temperature of 80 ℃ to obtain duck feather hydrolyzed sulfonated liquid, wherein the mass percentage of the duck feather is 30%, and the mass percentage of the sodium sulfite is 10%. And preparing the duck feather hydrolyzed sulfonated liquid, pig manure of a pig farm, coal and breeding wastewater of a grass carp farm into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the duck feather hydrolyzed sulfonated liquid to the pig manure of the pig farm to the coal to the breeding wastewater of the grass carp farm is 1: 5: 55: 39. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1300 ℃ and 3.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Example 3:

the materials selected in the embodiment are Shenhua coal, goose feather, cow dung of a dairy cow farm and breeding wastewater of a carp farm.

Goose feather, sodium sulfite and carp farm culture wastewater are heated and stirred for 6 hours at the temperature of 80 ℃ to obtain goose feather hydrolyzed sulfonated liquid, wherein the mass percentage of the goose feather is 30%, and the mass percentage of the sodium sulfite is 10%. And preparing the goose feather hydrolyzed sulfonated liquid, dairy cow dung, coal and carp farm breeding wastewater into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the goose feather hydrolyzed sulfonated liquid to the dairy cow dung to the coal to the carp farm breeding wastewater is 1: 5: 55: 39. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1300 ℃ and 3.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Example 4:

in the embodiment, the selected materials are Shenhua coal, chicken feather, chicken manure of a broiler chicken farm and eel farm culture wastewater.

Heating and stirring chicken feather, sodium sulfite and eel farm culture wastewater for 6 hours at the temperature of 80 ℃ to obtain chicken feather hydrolyzed sulfonated liquid, wherein the mass percentage of the chicken feather is 30 percent, and the mass percentage of the sodium sulfite is 10 percent. And preparing the chicken feather hydrolyzed sulfonated liquid, chicken manure in a broiler farm, coal and eel farm culture wastewater into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the chicken feather hydrolyzed sulfonated liquid to the chicken manure in the broiler farm to the coal to the eel farm culture wastewater is 1: 7: 55: 37. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1300 ℃ and 3.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Example 5:

in the embodiment, the selected materials are Shenhua coal, chicken feather, chicken manure of a broiler chicken farm and eel farm culture wastewater.

Heating and stirring chicken feather, sodium sulfite and eel farm culture wastewater for 6 hours at the temperature of 80 ℃ to obtain chicken feather hydrolyzed sulfonated liquid, wherein the mass percentage of the chicken feather is 30 percent, and the mass percentage of the sodium sulfite is 10 percent. And preparing the chicken feather hydrolyzed sulfonated liquid, chicken manure in a broiler farm, coal and eel farm culture wastewater into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the chicken feather hydrolyzed sulfonated liquid to the chicken manure in the broiler farm to the coal to the eel farm culture wastewater is 1: 9: 55: 35. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1300 ℃ and 3.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Example 6:

in the embodiment, the selected materials are Shenhua coal, chicken feather, chicken manure of a broiler chicken farm and eel farm culture wastewater.

Heating and stirring chicken feather, sodium sulfite and eel farm culture wastewater for 6 hours at the temperature of 80 ℃ to obtain chicken feather hydrolyzed sulfonated liquid, wherein the mass percentage of the chicken feather is 30 percent, and the mass percentage of the sodium sulfite is 10 percent. And preparing the chicken feather hydrolyzed sulfonated liquid, chicken manure in a broiler farm, coal and eel farm culture wastewater into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the chicken feather hydrolyzed sulfonated liquid to the chicken manure in the broiler farm to the coal to the eel farm culture wastewater is 1: 5: 55: 39. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1100 ℃ and 0.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Example 7:

in the embodiment, the selected materials are Shenhua coal, chicken feather, chicken manure of a broiler chicken farm and eel farm culture wastewater.

Heating and stirring chicken feather, sodium sulfite and eel farm culture wastewater for 6 hours at the temperature of 80 ℃ to obtain chicken feather hydrolyzed sulfonated liquid, wherein the mass percentage of the chicken feather is 30 percent, and the mass percentage of the sodium sulfite is 10 percent. And preparing the chicken feather hydrolyzed sulfonated liquid, chicken manure in a broiler farm, coal and eel farm culture wastewater into multi-element slurry in a rod mill by a wet method, wherein the mass ratio of the chicken feather hydrolyzed sulfonated liquid to the chicken manure in the broiler farm to the coal to the eel farm culture wastewater is 1: 5: 55: 39. the multi-element slurry is introduced into a gasification furnace to carry out gasification reaction at 1500 ℃ and 6.5 MPa. And obtaining the synthesis gas and the glassy state slag after chilling separation.

Comparative example 1

A common coal water slurry prepared by a conventional technique was used as a comparative example:

sodium lignosulfonate is used as a coal water slurry additive, clean industrial water is used for pulping, Shenhua coal is used as pulping coal, and a coal water slurry control slurry sample with the ratio of sodium lignosulfonate to coal to industrial water being 1: 60: 39 is prepared. And then the mixture is introduced into a gasification furnace to carry out gasification reaction at 1300 ℃ and 3.5 MPa.

The pulping performance and the recycling effect of each example and comparative example are shown in table 1.

TABLE 1

In Table 1, examples 1 to 7 are multi-component slurries in which feathers, livestock and poultry manure and aquaculture wastewater are comprehensively treated, and the slurry forming performance and the recycling effect of the coal water slurry comparative example and examples 1 to 7 are shown. As can be seen from the table, in comparative examples 1 to 7 and the comparative example of coal water slurry, it was found that the viscosity of the slurry of the obtained multicomponent slurry was increased and CO and H in the mixed gas obtained by gasification reaction were increased by using the sulfonated solution by hydrolysis of feathers in place of the additive of coal water slurry, using the waste water from aquaculture of aquatic products in place of the industrial clean water for pulping, using the excrements of livestock and poultry in place of part of the coal for pulping₂And the effective synthesis gas component is increased.

In conclusion, the comprehensive treatment and resource utilization method of the biomass waste provided by the invention is effective and feasible, and can realize changing waste into valuable while consuming various biomass wastes. The feather is used for preparing the hydrolyzed sulfonated liquid to replace a coal water slurry additive, the livestock manure is used for replacing part of raw material coal, the aquaculture wastewater is used for replacing industrial clean water, the multi-element slurry is prepared together, and gasification reaction is carried out in a gasification furnace, so that the pulping cost of the coal water slurry is reduced comprehensively while the biomass waste is utilized in a harmless and resource manner, and the environment-friendly benefit and the economic benefit are obvious.