阅读说明：本技术 一种复合生物质材料及其制备方法和应用 (Composite biomass material and preparation method and application thereof ) 是由 王长军 杨梦祺 于 2021-09-08 设计创作，主要内容包括：本发明公开了一种复合生物质材料,包括如下重量百分比的组分：漆渣：50％-90％；大豆秸秆：50％-10％。本发明还公开了所述的复合生物质材料用于作为火力发电的燃料的用途。本发明通过将漆渣和生物质原料合理复配,制备成复合生物质材料,能够作为火力发电燃料使用。不仅有效处理了漆渣废弃物,充分利用了其剩余价值,而且大大提高了生物质能的热能利用率,使生物质原料得到更有效利用。(The invention discloses a composite biomass material, which comprises the following components in percentage by weight: paint slag: 50% -90%; soybean straw: 50 to 10 percent. The invention also discloses application of the composite biomass material as a fuel for thermal power generation. According to the invention, the paint slag and the biomass raw materials are reasonably compounded to prepare the composite biomass material, and the composite biomass material can be used as a thermal power generation fuel. Not only effectively treats paint slag waste and makes full use of the residual value, but also greatly improves the heat energy utilization rate of biomass energy and enables the biomass raw material to be more effectively utilized.)

1. The composite biomass material is characterized by comprising the following components in percentage by weight:

paint slag: 50% -90%;

soybean straw: 50 to 10 percent.

2. The composite biomass material of claim 1, comprising the following components in weight percent:

paint slag: 70-90%;

soybean straw: 10 to 30 percent.

3. The composite biomass material of claim 1, comprising the following components in weight percent:

paint slag: 70 percent;

soybean straw: 30 percent.

4. The composite biomass material of any one of claims 1-3, further comprising MgO, wherein MgO is not less than 4% of the total amount of the paint slag and the soybean straw.

5. The composite biomass material of claim 4, wherein the MgO content is 4-5% of the total amount of the paint slag and the soybean straw.

6. A method for preparing the composite biomass material according to any one of claims 1 to 3, characterized in that the paint residue and the soybean straw are mixed according to the weight percentage of claims 1 to 3.

7. A method for preparing the composite biomass material according to any one of claims 1 to 5, characterized in that the paint residue, the soybean straw and MgO are mixed in the weight percentage according to claims 1 to 5.

8. Use of the composite biomass material according to any one of claims 1 to 5 as fuel for thermal power generation.

Technical Field

The invention belongs to the technical field of regeneration. In particular to a composite biomass material and a preparation method and application thereof.

Background

In the prior art, a large amount of paint mist is generated in the paint spraying process in the coating industry (particularly the automobile industry), and the conventional method for treating the paint mist is to gather the paint mist through a water curtain, then a flocculating agent (slag former) is added to condense the paint mist, so that paint drops lose viscosity, and paint slag floats upwards or sinks to form paint waste slag (paint slag for short). Paint slag is a complex organic compound, and the main components comprise paint itself, a small amount of external flocculant components and air or dust impurities in the environment where the paint is located, and a newly generated compound. In the oil paint, the content of aromatic hydrocarbon is more than 60%, and the content of various other ketone, ether and alcohol organic matters is about 20%. The flocculant mainly comprises two main inorganic flocculants of an aluminum salt system and an iron salt system. Paint residues contain a large amount of organic substances, and the compounds have certain toxicity to human beings and the environment. Studies have shown that even if the contents of the components are below their limits, many organic compounds mix and interact to form new compounds, which do not have relevant physicochemical data and often exhibit toxicity and irritation. It may cause immune disorders affecting the central nervous system, dizziness, headache, dizziness, lack of strength, chest distress etc., but also loss of digestive system, loss of appetite, nausea etc., in severe cases may damage liver and hematopoietic system, even cause death. At present, some paint residues are stored in a place and exposed in an open space, so that the environment is greatly damaged. In view of this, in 2008, paint residues were added to the chinese "national list of hazardous wastes", belonging to coating wastes.

According to the data of the China automobile industry Association, the total sale of the automobile market in China throughout 2015 is 2459.8 ten thousand. The total annual sales of 2016 Chinese automobiles is estimated to reach 2604 thousands, and at least 7.8 thousands of paint residues are generated according to the average generation of 3kg of paint residues per automobile. This is only a part of the total automotive industry that will produce several times as much paint residue, while other industries, in total, will produce tens of millions of tons of paint residue.

How to treat a large amount of paint slag is a very troublesome problem. At present, the domestic treatment method of the paint waste residue mainly comprises a landfill method, a pyrolysis incineration method and a recycling utilization method.

Landfill method

The paint slag landfill refers to a process of simply treating or solidifying paint slag, and then separating and burying the paint slag underground by taking certain measures. The landfill method has low cost and large capacity, but the landfill occupies excessive land resources, and paint slag percolate can be generated, and the paint slag percolate not only contains toxic heavy metal ions, but also contains a large amount of harmful organic components, is extremely complex, is accompanied by high chroma and emits strong smell. Therefore, the landfill method is easy to cause environmental pollution, especially the pollution of underground water, and greatly influences the living environment and sustainable development.

(II) pyrolysis incineration method

The main component of the paint slag is organic matter, so that the paint slag has a high heat value, and better energy can be obtained by burning the paint slag. Therefore, the incineration method is a basic method for treating the paint slag, can reduce the quantity of the paint slag, can be used as a usable fuel, can perform harmless treatment and reduce secondary pollution. The paint slag has high viscosity in a normal temperature environment, and the water in the paint slag is coated by the paint, so the paint slag is difficult to naturally evaporate and is difficult to simply break. Incineration consumes a lot of manpower and energy.

With the occurrence of scarcity of land, energy crisis, rising of energy price, and the like, disposal costs for landfill and incineration also increase greatly.

(III) cyclic regeneration and utilization

The principle of recycling is a mode of recycling useful components in the paint slag by adding a raw material such as resin. However, the main components of the paint waste residue are basically the same as those of crude oil paint, and molecules such as resin in the paint waste residue are not inactivated, which provides a premise for comprehensive utilization of the paint waste residue. The recycling of the paint slag is closely related to the internal component performance of the paint slag, if the molecular structure of the key components in the paint slag is damaged, the paint slag does not have the value of recoverable utilization, the paint slag cannot realize complete recycling by a certain method, and the influence of waste on the environment can be reduced only by degradation, pyrolysis, combustion and other methods.

Therefore, the research and development of the novel utilization process of the paint slag have very important social significance and economic significance.

The main fuel of the thermal power plant is coal, and the fuel cost can account for more than 60% of the production cost. However, the coal may contain miscellaneous stones and other impurities which do not generate heat but consume heat, which may increase the production cost of enterprises, and the combustion of coal may generate sulfur-containing gas, which may cause harm to the atmosphere, so that new energy sources should be sought as supplement of traditional energy sources as soon as possible.

The biomass fuel is a better choice for replacing the traditional fuel at the present stage. The biomass fuel is economical biomass briquette fuel which is mostly stem crops, peanut shells, barks and sawdustAnd lump fuel produced by processing solid waste (furfural residue, edible fungus residue and the like). The biomass energy has the advantages of large storage capacity, easy combustion, less pollution, low harmful components and more characteristic biomass energy fuel. CO released by combustion₂Substantially corresponding to the CO absorbed by photosynthesis during its growth₂So that CO is combusted when biomass energy is used₂The discharge amount of (A) can be considered as zero or even reduced (considering that the burnt plant ash contains a large amount of K)₂CO₃) This is incomparable with conventional energy sources such as gas, oil, coal, etc. Therefore, biomass energy has a very important position in the world energy structure, and particularly in vast rural areas and economically undeveloped areas, the application of the biomass energy still occupies a large proportion. The disadvantage of biomass energy is that the calorific value and thermal efficiency are low,

the volume is large, the transportation is not easy, and the thermal efficiency of directly burning the biomass is only 10% -30%, so the biomass fuel as the high-efficiency clean fuel must be processed and molded.

Disclosure of Invention

According to the invention, researches show that the paint slag can be used for replacing the position of coal in thermal power generation and can also exert the residual value of the paint slag. The characteristics of the paint slag obtained by the invention can replace coal to carry out thermal power generation by industrial analysis and element analysis of the paint slag. And then comparing the combustion characteristics of the two straws available in Xuzhou locality by using a method of combining the thermogravimetric curve and the micro-quotient thermogravimetric curve to obtain that the combustion characteristics of the soybean straws are stronger than those of the corn straws. In order to enable the paint slag fuel to be more favorable for caking, the soybean straws and the paint slag are mixed in proportion in the experiment, and the thermogravimetric experiment is utilized to compare the composite biomass fuel with the three proportions, so that the combustion characteristic of the composite biomass fuel can reach the best when the proportion of the paint slag and the soybean straws is 70%. In addition, in order to prevent the fuel ash from damaging the furnace body, MgO with a certain proportion is added into the fuel in the experiment, so that the melting point of the ash obtained by burning the fuel reaches over 1200 ℃, and finally the composite biomass fuel containing 4% of MgO and 70% of MgO can be used as the fuel in thermal power generation.

Accordingly, a first object of the present invention is to provide a composite biomass material, and a second object of the present invention is to provide a use of the composite biomass material.

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

as a first aspect of the present invention, a composite biomass material is characterized by comprising the following components by weight:

paint slag: 50% -90%;

soybean straw: 50 to 10 percent.

According to the invention, the composite biomass material comprises the following components in percentage by weight:

paint slag: 70-90%;

soybean straw: 10 to 30 percent.

Preferably, the composite biomass material comprises the following components in percentage by weight:

paint slag: 70 percent;

soybean straw: 30 percent.

According to the invention, the composite biomass material also comprises MgO, and the content of MgO is not less than 4% of the total amount of the paint residues and the soybean straws.

Furthermore, the MgO accounts for 4-5% of the total amount of the lacquer residues and the soybean straws.

As a second aspect of the invention, the preparation method of the composite biomass material is to mix the lacquer residue and the soybean straws according to the weight percentage.

According to the preparation method of the composite biomass material, the paint slag, the soybean straw and the MgO are mixed according to the weight percentage.

As a third aspect of the present invention, a use of the composite biomass material as a fuel for thermal power generation.

According to the present invention, said uses include, but are not limited to:

(1) non-renewable fossil fuel resources such as coal are replaced;

(2) reduction of atmospheric pollution, mainly including reduction of SO_XAnd NO_XContamination of the gas.

Compared with the prior art, the composite biomass material has the following beneficial technical effects:

(1) according to the invention, the paint slag and the biomass raw materials are reasonably compounded to prepare the composite biomass material, and the composite biomass material can be used as a thermal power generation fuel. Not only effectively treats paint slag waste and makes full use of the residual value, but also greatly improves the heat energy utilization rate of biomass energy and enables the biomass raw material to be more effectively utilized.

(2) Make full use of waste biomass and make the burning more abundant, compare pure biomass fuel, compound biomass material's combustion efficiency is higher, produces less ash simultaneously.

(3) After 4% -5% of MgO is added, the melting point of ash is effectively raised to be higher than 1200 ℃, and the ash is not condensed when the boiler is melted and at low temperature, so that the damage of boiler equipment is prevented, the service life of the boiler equipment is effectively prolonged, and the cost is reduced.

Drawings

FIG. 1 shows the thermogravimetric curve of a pure paint slag.

FIG. 2 is a microperimetric thermogram curve of pure paint slag.

FIG. 3 is a TG curve of corn stover in different atmospheres.

FIG. 4 is a DTG curve of corn stover in different atmospheres.

FIG. 5 is a TG curve of soybean straw under different atmospheres.

FIG. 6 is a DTG curve of soybean straw under different atmospheres.

Fig. 7 is a thermogravimetric plot of composite biomass material (50%).

Fig. 8 is a differential quotient thermogravimetric curve of a composite biomass material (50%).

Fig. 9 is a thermogravimetric plot of composite biomass material (70%).

Fig. 10 is a differential thermal gravimetry curve for composite biomass material (70%).

Fig. 11 is a thermogravimetric plot of a composite biomass material (90%).

Fig. 12 is a differential quotient thermogravimetric curve of a composite biomass material (90%).

FIG. 13 is a graph showing the relationship between ash softening temperature and MgO content.

Detailed Description

The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.

Industrial analysis and element analysis of paint waste residue

The paint slag used in the embodiment is produced by a finishing paint used by the xu-industry group (belonging to the heavy machinery industry and comprising finishing paints used by special vehicles such as cranes, excavators, fire trucks and the like), the chemical components of the finishing paint include natural resin modified by drying oil or semi-drying oil, artificial resin and synthetic resin, the colors and the varieties of the finishing paint are various, the use of the additive also enables the characteristics of the paint slag and the complexity of the components of the paint slag, and the content of aromatic hydrocarbon is more than 60%.

The industrial and elemental analyses of the paint slag showed the following results:

TABLE 1 results of elemental analysis of paint slag

TABLE 2 Industrial analysis results of paint sludge

In the table, k represents the mass fraction and the subscript ar represents the received base (the term of industrial analysis of coal, the received base means the coal in the received state as a reference). M represents moisture, A represents ash, V represents volatile matter, and C represents fixed carbon.

From the analysis result, the paint slag has higher volatile components and heat value, the low-level calorific value of the paint slag obtained by industrial analysis is 18.84MJ/kg, is equivalent to the heat value of coal used in a thermal power plant, can be used as thermal power generation fuel, and has good heat energy utilization value.

Example 1 Combustion characteristics of pure paint slag

The combustion of the pure paint slag in air was analyzed using an air atmosphere. The thermogravimetric curve (TG) is shown in FIG. 1, and the differential quotient thermogravimetric curve (DTG) is shown in FIG. 2.

As can be seen from FIGS. 1 and 2, when the pure paint slag is burned in an air atmosphere, the weight loss rate of the pure paint slag is obviously increased after the TG curve is 230 ℃; on the DTG curve, the fastest weight loss rate was at 325 ℃. It can be seen that after 230 ℃, the volatile matter starts to generate a combustion reaction under the air atmosphere, and the reaction heat generated in the combustion process accelerates the pyrolysis speed of the paint slag, so that the weight loss rate is accelerated. Therefore, the pure paint slag can generate flame combustion when heated to 230 ℃, and the combustion reaction can obviously accelerate the pyrolysis speed of the paint slag.

Example 2 preparation of composite Biomass Material

1. Selection of straw species

In the embodiment, the paint slag and the biomass are combined so as to achieve the purpose of fully utilizing the waste biomass and achieving the purpose of full combustion. In the embodiment, corn straw and soybean straw are selected for comparison, so that a better biomass material is selected to be matched with the paint slag.

Thermogravimetric analysis (TG) analysis and microtransom thermogravimetric analysis (DTG) analysis of corn stover. The results are shown in FIGS. 3-4.

Thermogravimetric analysis (TG) analysis and microtransom thermogravimetric analysis (DTG) analysis of soybean straw. The results are shown in FIGS. 5-6.

The results of fig. 3-4 show that: as can be seen from TG and DTG curves of the corn straws, the weight loss rate and the weight loss rate of the corn straws are different under different atmospheres. According to the DTG curve, the weight loss rate of the corn stalks in the oxygen atmosphere is obviously greater than that in the nitrogen atmosphere, and the reason is that when the temperature is about 270 ℃, volatile matters are generated in the oxygen atmosphere to generate combustion reaction, and the heat generated in the combustion process enables the pyrolysis rate of the corn stalks to be increased. Thus, in the case of corn stover being heated, open flame combustion occurs at around 270 ℃.

In comparison, the reaction time span under the nitrogen atmosphere is larger than that under the oxygen atmosphere, so that the combustion reaction can be judged to accelerate the pyrolysis process of the corn straws. As can be seen from the TG curve, the final weight loss ratio in the oxygen atmosphere is larger than that in the nitrogen atmosphere, which should be because the fixed carbon cannot be combusted due to the absence of oxygen after the pyrolysis is completed, and thus the remaining product is excessive compared with the product in the nitrogen atmosphere.

From a comparison of FIGS. 3-6, we have found that the open flame combustion temperature of soybean stover is slightly lower than that of corn stover by comparison with the curves of corn stover, indicating that soybean stover is more easily combusted than corn stover under heating; the reaction termination temperature of the corn stalks is higher than that of the soybean stalks, which indicates that the combustion of the corn stalks needs higher temperature, so that the reaction of the corn stalks is not easy to occur compared with the soybean stalks; and the reaction time of the corn straws is longer than that of the soybean straws.

In summary, compared with corn straw, soybean straw is more suitable for being used as biomass fuel to be matched with paint slag.

2. Mixing soybean straw with the paint slag.

In the embodiment, the soybean straw is used as the biomass fuel and is fully mixed with the paint slag to prepare the composite biomass material, and the combustion characteristic in the combustion process is analyzed through thermogravimetry so as to judge the feasibility of the soybean straw as the power generation fuel.

In the embodiment, the combustion characteristics of the composite biomass material in the combustion process are analyzed by adopting a thermogravimetric analysis (TG), the paint slag accounts for 90%, 70% and 50% (mass percent) respectively, and the paint slag is compared with pure paint slag and pure straws. The thermogravimetric curves and the differential quotient thermogravimetric curves (DTG curves) of the composite biomass material sample containing 50% of the paint slag are shown in fig. 7 and fig. 8, the thermogravimetric curves and the differential quotient thermogravimetric curves of the composite biomass material sample containing 70% of the paint slag are shown in fig. 9 and fig. 10, and the thermogravimetric curves and the differential quotient thermogravimetric curves of the composite biomass material sample containing 90% of the paint slag are shown in fig. 11 and fig. 12.

The result shows that when pure paint slag is combusted independently, the fuel is not easy to agglomerate, the volume is large, the transportation is not easy, the heat efficiency of directly combusting biomass is only 10-30%, and the biomass needs to be processed and molded; when the straw is independently used as fuel, the straw is influenced by regions and seasons, more gray matter is generated, the straw must be burnt in a furnace with a lower temperature, the combustion efficiency is low, and the advantages of biomass energy sources cannot be embodied. The combination of the two can make the fuel more easy machine-shaping, can burn under higher temperature simultaneously, effectively promotes combustion efficiency.

As can be seen from the comparison of fig. 1-2 with fig. 7-12, the combustion residual of the pure paint slag is reduced to about 30%, the combustion of the composite biomass material is more complete, and the combustion residual thereof is reduced to about 20%.

Compared with pure paint slag, the combustion temperature span of the composite biomass material is larger (the temperature span of the micro-quotient thermogravimetric curve of the pure paint slag is obviously smaller than that of the composite biomass fuel particles through curve comparison), which shows that the pyrolysis speed of the soybean straws is slower than that of the paint slag, so that the combustion time of the soybean straws in the furnace is longer.

As can be seen from the comparison of FIGS. 7 to 12, the pyrolysis temperature of the soybean straw and the paint residue are different, so two peaks appear, and the pyrolysis rate of the straw is reduced to some extent because the paint residue accounts for a higher proportion in the 70% and 90% samples.

3. Combustion characteristic parameter of composite biomass material

TABLE 3 Combustion characteristics of composite Biomass Material

In the table: t is_iThe initial reaction temperature is the initial precipitation temperature of volatile matters; t is_maxThe temperature corresponding to the maximum weight loss rate of the reaction; (dm/dT)_maxIs the maximum rate of weight loss; t is_fThe reaction completion temperature.

As can be seen from Table 3, the initial reaction temperature of the sample is higher than 70% when the composite biomass material contains 50% of paint slag, so that the 70% sample is easier to generate combustion reaction under heating condition; the reaction termination temperature of 50% of samples is also higher than that of 70% of samples, which indicates that the reaction time of 70% of samples is shorter than that of 50% of samples and the reaction is more violent; the maximum weight loss rate of the 50% sample is far less than that of the 70% sample, and the volatilization of the 70% sample is more violent.

As is apparent from Table 3, the composite biomass material contains 70% of the paint slag and 90% of the paint slag with the same combustion characteristics.

Example 3 Ash melting characteristics of composite Biomass Material

The biomass is mainly composed of hydrocarbon oxygen nitrogen alkali metals and other various trace elements, so that the biomass ash is mainly composed of various alkali metal salts and alkali metal oxides and various complex compounds. The presence of alkali metal salts and alkali metal oxides, among others, results in a relatively low melting temperature of the ash. Under the condition of high temperature, the alkali metal oxide and the alkali metal salt can generate complex chemical reaction with other substances to generate low-melting-point compounds, and the compounds exist in a molten state at the high temperature, and the molten compounds flow in a hearth to fuse some ash particles and are partially condensed into solids at the low temperature in the hearth. As the combustion progresses, these solids can build up in the furnace and become difficult to remove, eventually leading to damage to the thermal equipment and even dangerous accidents. To avoid the above problems, it is necessary to make the ash melting temperature higher than 1200 ℃.

The ashing temperature in the experiment is 600 ℃, in order to ensure complete combustion of biomass, the combustion is carried out in air, and the constant temperature is kept for one hour at 600 ℃. MgO was added as a catalyst in an amount of 3%, 4%, and 5% of the content of the composite biomass material, and the ash softening temperature was measured by an ash measuring instrument, and the results are shown in fig. 13.

As can be seen from fig. 13, the ash softening temperature of the 70% sample is about 700 ℃, the ash softening temperature of the 70% sample is increased by adding MgO, and the melting point can be made to be 1200 ℃ or higher when the MgO content reaches 4%, which satisfies the experimental requirements. The main reason is that MgO is an alkaline oxide, generally has a low ionic potential, can damage polymers, can damage some compounds with low melting points to form compounds with high melting points, has a high melting point, and can increase the melting point when the content of MgO is high.

Example 4 practical application

The paint slag composite biofuel is briquetted by a briquetting machine, so that the transportation, the storage and the use are convenient.

The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications or alterations to this practice will occur to those skilled in the art and are intended to be within the scope of this invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.