CN111440635A - Solid waste pyrolysis liquid phase product impurity removal and quality improvement method and product - Google Patents
Solid waste pyrolysis liquid phase product impurity removal and quality improvement method and product Download PDFInfo
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Abstract
The invention belongs to the field of solid waste treatment, and particularly discloses a solid waste pyrolysis liquid phase product impurity removal and quality improvement method and a product. The method specifically comprises the following steps: mixing a lithium system molten salt temperature regulating agent and calcium-magnesium composite molten salt to obtain a primary molten salt system, introducing a solid waste pyrolysis liquid phase product into the primary molten salt system, heating and preserving heat for a preset time, so as to realize low-temperature impurity removal and obtain a primary liquid phase product; mixing a transition metal catalyst and sodium-potassium composite molten salt to obtain a second-level molten salt system, introducing a first-level liquid-phase product into the second-level molten salt system, heating and preserving heat for a preset time, so as to realize high-temperature upgrading and obtain a second-level liquid-phase product; and condensing and separating the secondary liquid phase product, and respectively collecting uncondensed gas and a clean homogenized liquid phase product. According to the invention, the solid waste pyrolysis liquid phase product is subjected to grading treatment by adopting a molten salt cascade treatment method, so that the generation of pollutants is reduced, the production efficiency is improved, and meanwhile, the effective treatment of the solid waste pyrolysis liquid phase product is realized.
Description
Technical Field
The invention belongs to the field of solid waste treatment, and particularly relates to a solid waste pyrolysis liquid phase product impurity removal and quality improvement method and a product.
Background
The urban solid waste has huge yield which exceeds 20000 ten thousand tons/year, and from the environmental and economic viewpoints, the solid waste disposal in China becomes a problem to be solved urgently. The pyrolysis technology is one of effective ways for disposing urban solid wastes, and can convert the solid wastes into multiphase products with potential utilization values, such as combustible gas, active coke, liquid-phase products and the like. Wherein, the pyrolysis liquid phase product not only can be used as fuel, but also can provide raw materials for aromatic chemical industry and special chemicals. Different from the utilization of combustible gas and active coke, the components of the solid waste pyrolysis liquid phase product after pyrolysis treatment are more complex, the detectable substance types can reach more than two hundred, the detectable substance types comprise hydrocarbons with high aromaticity and derivatives thereof, such as benzene, phenol, aldehyde ketone, carboxylic acid, polycyclic aromatic hydrocarbon, oxygen-containing derivatives, nitrogen-containing derivatives, chlorine-containing derivatives, sulfur-containing derivatives and the like, the direct use of the solid waste pyrolysis oil is influenced by the huge difference of raw materials and the migration and transformation of partial residues such as N, S, Cl, and a plurality of environmental pollution problems also exist in the aspect of further resource utilization. If the pyrolysis liquid phase product is directly used for combustion, the disadvantages are many, such as strong corrosivity, poor thermal stability, high viscosity and the like. Therefore, in view of energy fuel utilization and environmental protection requirements, the removal of impurities and the quality improvement of the solid waste pyrolysis liquid phase products are particularly necessary from the development direction.
In various treatment modes for pyrolysis liquid phase products, an effective separation and purification way is searched for and is the core of resource utilization, and effective impurity removal and quality improvement of the synthetic and modified catalyst in the conversion process is the key of energy utilization. Based on such application background, the currently mainstream pyrolysis liquid phase product treatment modes include a component distillation separation technology, a tar catalytic hydrodeoxygenation technology and a tar catalytic cracking deoxygenation technology which aim at component separation. Patent CN1676583A describes a medium-high temperature coal tar hydrocracking process, in which medium-high temperature coal tar is introduced into a heating furnace to mix with hydrogen, and the mixture is fed into a hydrofining reactor, and the hydrogen separated by the high pressure separator after heat exchange is fed back to the hydrofining reactor by a recycle hydrogen compressor, and the produced oil is fed into a low pressure separator, and the treated low fraction fuel oil is fed into a deoxygenating tower, and further fed into a fractionating tower after fuel gas is removed, and fractionated to obtain gasoline, diesel oil and lubricating oil, and tail oil is fed into a hydrocracking reactor. In the patent, the high-temperature coal tar contains a large amount of metals and other components which are easy to cause catalyst deactivation and bed pressure drop increase, and the components are directly treated by a traditional hydrofining reactor without pre-treating raw materials, so that the catalyst deactivation speed is accelerated, the bed pressure drop is increased, and the running period of the device is shortened. Further, in addition to the above, publication No. CN101918133A provides a method for producing a reforming catalyst for tar-containing gas, a method for reforming tar, and a method for regenerating a reforming catalyst for tar-containing gas, wherein a precipitant is used to form a precipitate in a solution of nickel and magnesium, the precipitate is dried and calcined to form oxides of nickel and magnesium, alumina and water or an alumina sol are added thereto and mixed, and the mixture is at least dried and calcined to produce a catalyst, and thermal decomposition tar of a carbonaceous raw material is reformed and gasified. The patent has higher requirements on the performance of the catalyst in the treatment of pyrolysis liquid phase products, and also has the problems of inevitable carbon deposition inactivation and the like of the catalyst, thereby increasing the economic cost.
The invention patent of publication No. CN109749758A provides a tar quality improvement treatment method, which mainly comprises mixing a tar raw material and micromolecular alcohol, and introducing the mixture into a solid acid catalyst, wherein aromatic hydrocarbon and phenol components in the tar raw material and the micromolecular alcohol are subjected to high-temperature gas-phase catalytic conversion reaction under the catalytic action of the solid acid catalyst to obtain a gas-phase product. The tar and the micromolecular alcohol are mixed and then subjected to high-temperature gas phase catalytic conversion, aromatic hydrocarbon and hetero-phenol components in the tar react with the micromolecular alcohol by utilizing a solid acid catalyst, and the aromatic hydrocarbon and the phenol in the tar are converted into high-value products taking pentamethylbenzene, hexamethylbenzene, pentaethylbenzene or hexaethylbenzene as main components. Meanwhile, a small amount of micromolecule oxygen-containing components contained in the tar are subjected to deoxidation conversion, and products such as low-boiling-point alkane, condensed cyclic hydrocarbon and the like and gas products with higher calorific values are obtained. However, for the full-component pyrolysis liquid-phase product, the method does not cause the tar component to tend to be converted into a more complex structure, and causes inconvenience for further separation and utilization.
Disclosure of Invention
Aiming at the defects and/or improvement requirements in the prior art, the invention provides a solid waste pyrolysis liquid phase product impurity removal and quality improvement method and a solid waste pyrolysis liquid phase product impurity removal and quality improvement product, wherein the targets of stage treatment and stage conversion of the solid waste pyrolysis liquid phase product are realized by adopting a molten salt step treatment mode, and the solid waste pyrolysis liquid phase product is subjected to low-temperature impurity removal and high-temperature quality improvement by utilizing the melting characteristics of different molten salt systems, so that the generation of pollutants is reduced, the production efficiency is improved, and the effective treatment of the solid waste pyrolysis liquid phase product is effectively realized.
In order to achieve the purpose, according to one aspect of the invention, an impurity removal and quality improvement method for solid waste pyrolysis liquid phase products is provided, and the method comprises the following steps:
s1, mixing a lithium system molten salt temperature control agent and calcium-magnesium composite molten salt to obtain a primary molten salt system, introducing a solid waste pyrolysis liquid phase product into the primary molten salt system, heating to a preset temperature, and preserving heat for a preset time, so as to realize low-temperature impurity removal and obtain a primary liquid phase product;
s2, mixing a transition metal catalyst and sodium-potassium composite molten salt to obtain a secondary molten salt system, introducing the primary liquid phase product into the secondary molten salt system, heating to a preset temperature, and preserving heat for a preset time, so as to realize high-temperature upgrading and obtain a secondary liquid phase product;
s3, the secondary liquid phase product is condensed and separated, and the uncondensed gas and the clean homogenized liquid phase product are collected respectively.
Further preferably, in step S1, the lithium-based molten salt temperature control agent includes L iOH and L iHCO3One or two of them; the calcium-magnesium composite molten salt comprises Ca (OH)2And Mg (OH)2。
Further preferably, in step S1, the mass ratio of the lithium-based molten salt temperature control agent to the calcium-magnesium composite molten salt in the primary molten salt system is 1:2 to 1: 4.
More preferably, in step S1, the heating temperature is 400 to 600 ℃ and the holding time is 20 to 60 min.
Further preferably, in step S2, the transition metal catalyst includes one or more of iron carbonate, chromium carbonate and nickel carbonate, and the particle size of the transition metal catalyst is 100 to 400 mesh; the sodium-potassium composite molten salt comprises Na2CO3And K2CO3。
Further preferably, in step S2, the mass ratio of the transition metal catalyst to the sodium-potassium composite molten salt in the secondary molten salt system is 1:4 to 1: 9.
More preferably, in step S2, the heating temperature is 600 to 800 ℃ and the holding time is 20 to 120 min.
As a further preference, in step S1, the solid waste pyrolysis liquid phase product is introduced into the primary molten salt system by means of carrying with a carrier gas; in step S2, introducing the primary liquid-phase product into the secondary molten salt system by means of carrier gas entrainment; the carrier gas is one or two of helium and argon.
According to another aspect of the invention, impurity removal is provided by utilizing the solid waste pyrolysis liquid phase productFuel gas and chemical products prepared by the quality-improving method, wherein the fuel gas is uncondensed gas and comprises H2、CH4And CO; the chemical product is a clean homogenized liquid phase product, and comprises one or more of benzene, toluene, xylene, monophenol and furfural.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. according to the invention, the solid waste pyrolysis liquid phase product is subjected to grading treatment by adopting a molten salt gradient treatment method, and low-temperature impurity removal and high-temperature quality improvement are performed on the solid waste pyrolysis liquid phase product by utilizing molten salt systems with different melting characteristics, so that the generation of pollutants is reduced, the production efficiency is improved, and meanwhile, the effective treatment of the solid waste pyrolysis liquid phase product is realized; the calcium-magnesium composite molten salt in the primary molten salt system effectively solves the problem that the solid hydroxide is insufficient in removing sulfur, chlorine and other polluted gases, the calcium-magnesium ions and tar gas molecules are subjected to gas-liquid reaction by utilizing a molten salt liquid environment with good fluidity, the reaction contact area is increased, the effective absorption of polluting elements is ensured, meanwhile, the low-melting-point characteristic of the lithium system molten salt temperature regulating agent makes up the characteristics of high melting point and high-temperature reaction of the molten salt system, and the energy requirement of the reaction system is reduced; the transition metal catalyst in the secondary molten salt system is uniformly dispersed by means of the good fluidity of the molten salt system, the catalytic efficiency of the transition metal catalyst on solid waste pyrolysis tar gaseous molecules is effectively improved, the catalytic conversion of the molten salt system is further enhanced, and meanwhile, the molten environment provided by the molten salt reduces the attached collection of carbon deposition on the catalyst, so that more carbon deposition is deposited at the bottom of the molten salt system, and the catalytic activity of the molten salt system is maintained;
2. meanwhile, the types and the mixing mass ratio of the lithium system molten salt and the calcium-magnesium composite molten salt are optimized, so that the precipitation leaching of the conversion product from a primary molten salt system after impurity removal can be effectively realized, the movement of reaction balance to the product generation direction is promoted, and the impurity removal rate of the solid waste pyrolysis liquid phase product is improved;
3. in addition, the invention can ensure the thermal stability of the secondary molten salt catalytic system at high temperature and the good reaction characteristic of the catalyst by optimizing the types of the transition metal catalyst, the sodium-potassium composite molten salt and the mixing mass ratio thereof.
Drawings
FIG. 1 is a schematic flow chart of a solid waste pyrolysis liquid phase product impurity removal and upgrading method provided by the preferred embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in FIG. 1, the embodiment of the invention provides a solid waste pyrolysis liquid phase product impurity removal and quality improvement method, which comprises the following steps:
s1, mixing a lithium system molten salt temperature control agent and calcium-magnesium composite molten salt to obtain a primary molten salt system, introducing a solid waste pyrolysis liquid phase product into the primary molten salt system in a carrier gas carrying mode, heating to a preset temperature, and preserving heat for a preset time to realize low-temperature impurity removal and obtain a primary liquid phase product, wherein the carrier gas is one or two of helium and argon;
s2, mixing a transition metal catalyst and sodium-potassium composite molten salt to obtain a secondary molten salt system, introducing a primary liquid-phase product into the secondary molten salt system in a carrier gas carrying manner, heating to a preset temperature, and preserving heat for a preset time, so as to realize high-temperature upgrading and obtain a secondary liquid-phase product, wherein the carrier gas is one or two of helium and argon;
s3, the secondary liquid phase product is condensed and separated, and the uncondensed gas and the clean homogenized liquid phase product are collected respectively.
Further, in step S1, the lithium-based molten salt temperature control agent includes L iOH and L iHCO3One or two of them, the low melting point characteristic is used for compensating the molten saltThe high melting point and high temperature reaction characteristics of the system effectively reduce the energy requirement of the reaction system, thereby realizing low-temperature impurity removal; the calcium-magnesium composite molten salt comprises Ca (OH)2And Mg (OH)2The gas-liquid reaction is carried out between the molten salt liquid environment with good fluidity and tar gas molecules, the reaction contact area is increased, and the effective absorption of polluting elements is ensured, so that the problem that the solid hydroxide is insufficient in removing the polluted gases such as sulfur and chlorine is solved; the mass ratio of the lithium-system molten salt temperature regulating agent to the calcium-magnesium composite molten salt in the primary molten salt system is 1: 2-1: 4, so that the temperature regulation of the molten salt system is ensured, a large amount of calcium-magnesium ions are combined with impurity molecules, the precipitation leaching of a product from the primary molten salt system after impurity removal is effectively realized, and the movement of reaction balance to the product generation direction is promoted.
Further, in step S1, the heating temperature is 400 to 600 ℃, and the holding time is 20 to 60min, thereby avoiding the problem of insufficient reaction caused by viscosity increase due to too low temperature and the quality loss of the reaction system caused by decomposition of the molten salt system due to too high temperature, and simultaneously, the proper holding time promotes effective removal of impurities, and on the other hand, the crosslinking reaction of other products caused by too long holding time is avoided.
Further, in step S2, the transition metal catalyst includes one or more of iron carbonate, chromium carbonate and nickel carbonate, the particle size of the transition metal catalyst is 100-400 meshes, iron, chromium and nickel with catalytic activity enter the secondary molten salt system in the form of carbonate particles, and are decomposed at high temperature to generate more iron, chromium and nickel composite oxide catalysts, uniform dispersion is achieved by virtue of better fluidity of the molten salt system, efficient conversion of solid waste pyrolysis tar gaseous molecules by the catalyst carried by the molten salt system is effectively achieved, and catalytic conversion of the molten salt system is further enhanced; the sodium-potassium composite molten salt comprises Na2CO3And K2CO3The enrichment of carbon deposition on the catalyst can be reduced by providing a molten state environment, so that more carbon deposition is deposited at the bottom of the molten salt system, and the catalytic activity of the molten salt system is maintained; transition metal catalyst and sodium-potassium complex in secondary molten salt systemThe mass ratio of the fused salt is 1: 4-1: 9, so that a high-temperature fused salt carrier taking potassium and sodium as main bodies is provided, and the thermal stability of a secondary fused salt catalytic system at high temperature and the good reaction characteristic of the catalyst are ensured.
Further, in step S2, the heating temperature is 600 to 800 ℃, and the holding time is 20 to 120min, so as to avoid the problems of the increase of heat transfer and mass transfer resistance of the secondary molten salt system caused by the decrease of heat capacity and the increase of density of the secondary molten salt system due to too low reaction temperature, and further the problems of uneven dispersion and low reactivity of the catalyst, on the other hand, the quality loss of the reaction system caused by the decomposition of the molten salt system caused by too high temperature, and in addition, the secondary reaction of the product caused by too long holding time can be avoided due to proper reaction time.
The method provided by the invention is easy to control, the impurity removal and quality improvement efficiency index of the reaction can be changed in real time only by controlling the reaction temperature, the reaction time and the mixing proportion of raw materials at all levels, the industrial continuous production is easy to realize, in addition, the molten salt system can be recycled through proper regeneration treatment, and the method has better production economy.
According to another aspect of the invention, fuel gas and chemical products prepared by the solid waste pyrolysis liquid phase product impurity removal and quality improvement method are provided, and the fuel gas is uncondensed gas and comprises H2、CH4And CO; the chemical product is a clean homogenized liquid phase product, which comprises one or more of benzene, toluene, xylene, monophenol and furfural.
The method for removing impurities and improving quality of the solid waste pyrolysis liquid phase product provided by the invention is further explained according to specific examples.
Example 1
(a) L iOH and L iHCO were mixed3Mixing according to the mass ratio of 1:1 to obtain the lithium molten salt temperature regulating agent, and mixing Ca (OH)2And Mg (OH)2Mixing the calcium-magnesium composite molten salt according to the mass ratio of 1:1 to obtain calcium-magnesium composite molten salt, and then mixing the lithium system molten salt temperature control agent and the calcium-magnesium composite molten salt according to the mass ratio of 1:2 to obtain a primary molten salt system;
(b) introducing a mixture of the wood chip pyrolysis liquid phase product and the rubber pyrolysis liquid phase product into a primary molten salt system in an argon carrying mode, heating to 400 ℃, and preserving heat for 40min, so as to realize low-temperature impurity removal and obtain a primary liquid phase product;
(c) mixing Fe2(CO3)3：Cr2O3·xCO2·yH2O：NiCO3According to the following steps: 1:1 to obtain a transition metal catalyst, adding Na2CO3And K2CO3Mixing according to the mass ratio of 1:1 to obtain sodium-potassium composite molten salt, and then mixing 100-200-mesh transition metal catalyst and the sodium-potassium composite molten salt according to the mass ratio of 1:4 to obtain a secondary molten salt system;
(d) introducing the primary liquid phase product into a secondary molten salt system in an argon carrying mode, heating to 600 ℃, and preserving heat for 120min, so as to realize high-temperature upgrading and obtain a secondary liquid phase product;
(e) and condensing and separating the secondary liquid phase product, and respectively collecting uncondensed gas and a clean homogenized liquid phase product.
Table 1 shows the content change of the pollutants in the solid waste pyrolysis liquid phase product before the step treatment and the clean homogenized liquid phase product after the step treatment, and it can be known from the results in table 1 that the sulfur content in the liquid phase product is reduced by 2.54% and the chlorine content is reduced by 1.68% after the treatment of the first-stage molten salt system; after the treatment of the secondary molten salt system, the furan content is reduced by 5.1%, the thiophene content is reduced by 4.54%, and the BTX content is improved by 30.18%.
TABLE 1 variation of product content of solid waste pyrolysis liquid phase product fused salt gradient impurity removal upgrading
Example 2
(a) L iOH single substance is used as lithium series molten salt temperature regulator, Ca (OH)2And Mg (OH)2Mixing the calcium-magnesium composite molten salt according to the mass ratio of 1:1 to obtain calcium-magnesium composite molten salt, and then mixing the lithium system molten salt temperature control agent and the calcium-magnesium composite molten salt according to the mass ratio of 1:4 to obtain a primary molten salt system;
(b) introducing a mixture of the wood chip pyrolysis liquid-phase product and the plastic pyrolysis liquid-phase product into a primary molten salt system in an argon carrying mode, heating to 600 ℃, and preserving heat for 20min, so as to realize low-temperature impurity removal and obtain a primary liquid-phase product;
(c) mixing Fe2(CO3)3：NiCO3According to the following steps: 1 to obtain a transition metal catalyst, adding Na2CO3And K2CO3Mixing according to the mass ratio of 1:1 to obtain sodium-potassium composite molten salt, and then mixing 200-400-mesh transition metal catalyst and the sodium-potassium composite molten salt according to the mass ratio of 1:6 to obtain a secondary molten salt system;
(d) introducing the primary liquid phase product into a secondary molten salt system in an argon carrying mode, heating to 800 ℃, and preserving heat for 20min, so as to realize high-temperature upgrading and obtain a secondary liquid phase product;
(e) and condensing and separating the secondary liquid phase product, and respectively collecting uncondensed gas and a clean homogenized liquid phase product.
Table 2 shows the variation of the content of contaminants in the solid spent pyrolysis liquid phase product before the cascade treatment and the clean homogenized liquid phase product after the cascade treatment.
TABLE 2 variation of product content of solid waste pyrolysis liquid phase product fused salt gradient impurity removal upgrading
From the results in table 2, it can be seen that the sulfur content in the liquid phase product is reduced by 1.51% and the chlorine content is reduced by 1.34% after the treatment of the first-stage molten salt system; after the treatment of the secondary molten salt system, the furan content is reduced by 9.41 percent, the thiophene content is reduced by 0.52 percent, and the BTX content is improved by 47.07 percent
Example 3
(a) L iHCO3The single substance is used as a lithium-based molten salt temperature regulator, Ca (OH)2And Mg (OH)2Mixing the calcium-magnesium composite molten salt according to the mass ratio of 2:1 to obtain calcium-magnesium composite molten salt, and mixing the lithium system molten salt temperature control agent and the calcium-magnesium composite molten salt according to the mass ratio of 2:5 to obtain the calcium-magnesium composite molten saltObtaining a first-level molten salt system;
(b) introducing a mixture of the wood chip pyrolysis liquid-phase product, the plastic pyrolysis liquid-phase product and the rubber pyrolysis liquid-phase product into a primary molten salt system in a helium carrying manner, heating to 600 ℃, and preserving heat for 30min, so as to realize low-temperature impurity removal and obtain a primary liquid-phase product;
(c) mixing NiCO3A single substance as a transition metal catalyst, Na2CO3And K2CO3Mixing according to the mass ratio of 1:1 to obtain sodium-potassium composite molten salt, and then mixing 100-200-mesh transition metal catalyst and the sodium-potassium composite molten salt according to the mass ratio of 1:4 to obtain a secondary molten salt system;
(d) introducing the primary liquid-phase product into a secondary molten salt system in a helium carrying manner, heating to 800 ℃ and preserving heat for 20min, so as to realize high-temperature upgrading and obtain a secondary liquid-phase product;
(e) and condensing and separating the secondary liquid phase product, and respectively collecting uncondensed gas and a clean homogenized liquid phase product.
TABLE 3 variation of product content of solid waste pyrolysis liquid phase product fused salt gradient impurity removal upgrading
Table 3 shows the content change of the pollutants in the solid waste pyrolysis liquid phase product before the step treatment and the clean homogenized liquid phase product after the step treatment, and it can be known from the results in table 3 that the sulfur content in the liquid phase product is reduced by 2.13% and the chlorine content is reduced by 1.58% after the treatment of the first-stage molten salt system; after the treatment of the secondary molten salt system, the furan content is reduced by 5.56%, the thiophene content is reduced by 2.76%, and the BTX content is improved by 28.78%.
Example 4
(a) L iOH and L iHCO were mixed3Mixing according to the mass ratio of 1:1 to obtain the lithium molten salt temperature regulating agent, and mixing Ca (OH)2And Mg (OH)2Mixing the calcium-magnesium composite molten salt according to the mass ratio of 1:1, and then mixing the lithium system molten salt temperature control agent and the calcium-magnesium composite molten salt according to the mass ratio of 1:3 to obtain the calcium-magnesium composite molten saltA first-order molten salt system;
(b) introducing a mixture of a plastic pyrolysis liquid-phase product and a rubber pyrolysis liquid-phase product into a primary molten salt system in an argon carrying manner, heating to 400 ℃, and preserving heat for 20min, so as to realize low-temperature impurity removal and obtain a primary liquid-phase product;
(c) mixing Cr2O3·xCO2·yH2O：NiCO3According to the following steps: 1 to obtain a transition metal catalyst, adding Na2CO3And K2CO3Mixing according to the mass ratio of 1:1 to obtain sodium-potassium composite molten salt, and then mixing 100-200-mesh transition metal catalyst and the sodium-potassium composite molten salt according to the mass ratio of 1:9 to obtain a secondary molten salt system;
(d) introducing the primary liquid phase product into a secondary molten salt system in an argon carrying mode, heating to 700 ℃, and preserving heat for 120min, so as to realize high-temperature upgrading and obtain a secondary liquid phase product;
(e) and condensing and separating the secondary liquid phase product, and respectively collecting uncondensed gas and a clean homogenized liquid phase product.
Table 4 shows the content change of the pollutants in the solid waste pyrolysis liquid phase product before the step treatment and the clean homogenized liquid phase product after the step treatment, and it can be known from the results in table 4 that the sulfur content in the liquid phase product is reduced by 1.62% and the chlorine content is reduced by 0.98% after the treatment of the first-stage molten salt system; after the treatment of the secondary molten salt system, the furan content is reduced by 2.12%, the thiophene content is reduced by 5.99%, and the BTX content is improved by 19.92%.
TABLE 4 variation of product content of fused salt gradient impurity removal and quality improvement of solid waste pyrolysis liquid phase product
Example 5
(a) L iOH and L iHCO were mixed3Mixing according to the mass ratio of 2:1 to obtain the lithium-based molten salt temperature regulator, and mixing Ca (OH)2And Mg (OH)2Mixing the calcium and magnesium composite molten salt according to the mass ratio of 1:1 to obtain the calcium and magnesium composite molten salt, and then mixing the temperature regulating agent and the lithium system molten saltMixing the calcium-magnesium composite molten salt according to the mass ratio of 1:2 to obtain a primary molten salt system;
(b) introducing a mixture of the wood chip pyrolysis liquid-phase product, the plastic pyrolysis liquid-phase product and the rubber pyrolysis liquid-phase product into a primary molten salt system in an argon carrying mode, heating to 500 ℃, and preserving heat for 60min, so as to realize low-temperature impurity removal and obtain a primary liquid-phase product;
(c) mixing Fe2(CO3)3：Cr2O3·xCO2·yH2O is as follows: 1 to obtain a transition metal catalyst, adding Na2CO3And K2CO3Mixing according to the mass ratio of 1:1 to obtain sodium-potassium composite molten salt, and then mixing 200-400-mesh transition metal catalyst and the sodium-potassium composite molten salt according to the mass ratio of 1:7 to obtain a secondary molten salt system;
(d) introducing the primary liquid phase product into a secondary molten salt system in an argon carrying mode, heating to 800 ℃, and preserving heat for 60min, so as to realize high-temperature upgrading and obtain a secondary liquid phase product;
(e) and condensing and separating the secondary liquid phase product, and respectively collecting uncondensed gas and a clean homogenized liquid phase product.
Table 5 shows the content change of the pollutants in the solid waste pyrolysis liquid phase product before the step treatment and the clean homogenized liquid phase product after the step treatment, and it can be known from the results in table 5 that the sulfur content in the liquid phase product is reduced by 2.31% and the chlorine content is reduced by 1.26% after the treatment of the first-stage molten salt system; after the treatment of the secondary molten salt system, the furan content is reduced by 3.86%, the thiophene content is reduced by 3.22%, and the BTX content is improved by 28.71%.
TABLE 5 variation of product content of solid waste pyrolysis liquid phase product fused salt gradient impurity removal upgrading
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
Claims (9)
1. The impurity removal and quality improvement method for the solid waste pyrolysis liquid phase product is characterized by comprising the following steps:
s1, mixing a lithium system molten salt temperature control agent and calcium-magnesium composite molten salt to obtain a primary molten salt system, introducing a solid waste pyrolysis liquid phase product into the primary molten salt system, heating to a preset temperature, and preserving heat for a preset time, so as to realize low-temperature impurity removal and obtain a primary liquid phase product;
s2, mixing a transition metal catalyst and sodium-potassium composite molten salt to obtain a secondary molten salt system, introducing the primary liquid phase product into the secondary molten salt system, heating to a preset temperature, and preserving heat for a preset time, so as to realize high-temperature upgrading and obtain a secondary liquid phase product;
s3, the secondary liquid phase product is condensed and separated, and the uncondensed gas and the clean homogenized liquid phase product are collected respectively.
2. The solid waste pyrolysis liquid phase product impurity removal and quality improvement method of claim 1, wherein in step S1, the lithium-based molten salt temperature regulator comprises L iOH and L iHCO3One or two of them; the calcium-magnesium composite molten salt comprises Ca (OH)2And Mg (OH)2。
3. The impurity removal and quality improvement method for the solid waste pyrolysis liquid phase product according to claim 1, wherein in step S1, the mass ratio of the lithium-based molten salt temperature control agent to the calcium-magnesium composite molten salt in the primary molten salt system is 1: 2-1: 4.
4. The method for removing impurities and improving quality of the solid waste pyrolysis liquid phase product according to claim 1, wherein in the step S1, the heating temperature is 400-600 ℃, and the holding time is 20-60 min.
5. The method for removing impurities and improving quality of solid waste pyrolysis liquid phase products as claimed in claim 1, wherein the method is characterized in thatIn step S2, the transition metal catalyst includes one or more of iron carbonate, chromium carbonate, and nickel carbonate, and the particle size of the transition metal catalyst is 100-400 mesh; the sodium-potassium composite molten salt comprises Na2CO3And K2CO3。
6. The impurity removal and quality improvement method for the solid waste pyrolysis liquid phase product according to claim 1, wherein in step S2, the mass ratio of the transition metal catalyst to the sodium-potassium composite molten salt in the secondary molten salt system is 1: 4-1: 9.
7. The method for removing impurities and improving quality of the solid waste pyrolysis liquid phase product according to claim 1, wherein in the step S2, the heating temperature is 600-800 ℃, and the holding time is 20-120 min.
8. The impurity removing and quality improving method for the solid waste pyrolysis liquid phase product according to any one of claims 1 to 7, wherein in step S1, the solid waste pyrolysis liquid phase product is introduced into the primary molten salt system by carrying with carrier gas; in step S2, introducing the primary liquid-phase product into the secondary molten salt system by means of carrier gas entrainment; the carrier gas is one or two of helium and argon.
9. The fuel gas and the chemical products prepared by the solid waste pyrolysis liquid phase product impurity removal and quality improvement method according to any one of claims 1 to 8, wherein the fuel gas is uncondensed gas comprising H2、CH4And CO; the chemical product is a clean homogenized liquid phase product, and comprises one or more of benzene, toluene, xylene, monophenol and furfural.
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| CN109530386A (en) * | 2018-10-24 | 2019-03-29 | 华中科技大学 | A method of based on fused salt multistage upgrading mixing organic solid castoff |
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