CN115895736A - Method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin - Google Patents
Method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin Download PDFInfo
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Abstract
The invention discloses a method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin. The method comprises the following steps: pyrolysis and gasification: mixing the pretreated waste plastics with alkali lignin, and carrying out pyrolysis gasification to generate a gas-phase product, a liquid-phase product and a solid-phase product; adding a catalyst into the liquid-phase product for catalytic conversion to obtain an olefin product; carrying out chemical chain reforming on the gas-phase product and an oxygen carrier, and then reacting with steam to obtain hydrogen; and calcining the reacted oxygen carrier in an air atmosphere, and performing a circulating reaction in the step S3. According to the invention, the alkali lignin and the waste plastics are mixed for pyrolysis and gasification, and the catalytic synergistic effect is generated by utilizing the alkali metals such as Na and Al in the alkali lignin to the pyrolysis and gasification of the waste plastics, so that the recovery yield of olefin in the waste plastics is improved, the added value of the product is improved, the synergistic resource utilization of the waste is realized, and the high-efficiency, clean and high-value utilization of the waste plastics is realized.
Description
Technical Field
The invention belongs to the technical field of waste plastic recycling, and particularly relates to a method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin.
Background
Plastics are important organic synthetic polymer materials and are widely applied, and waste plastics are a general name of plastics eliminated or replaced in industrial production and daily life of people and comprise waste plastic films, plastic wires and woven products, plastic packing cases and containers, plastic bags, mulching films and the like. In addition, plastics for automobiles, electronic appliances and household electrical appliances in China also become one of the important sources of waste plastics. The rapid increase of the yield of waste plastics causes a series of social problems, and the vigorous development of the waste plastics recycling industry is imperative.
The alkali lignin is a byproduct generated after cellulose is separated from plants in the paper industry, and is rich in lignin, alkali metal and inorganic salt components. The yield of alkali lignin in China is huge, about 3000 ten thousand tons of cellulose are separated from plants every year in the paper making industry, and about 1000 ten thousand tons of alkali lignin by-products are obtained simultaneously. The alkali lignin directly used as fuel has low combustion heat value, is easy to corrode a boiler and pipeline equipment, and has an alkali metal treatment bottleneck in the recycling process. At present, only a small part of alkali lignin is prepared into high-added-value products such as a water reducing agent, a dispersing agent and the like through reaction processes such as oxidation, sulfonation and the like, most of alkali lignin is abandoned or concentrated to be used as auxiliary fuel, and not only is huge resource waste caused, but also environmental threat exists.
On the other hand, the low-carbon olefins (ethylene, propylene, butylene) are important platform compounds, are important raw materials and intermediates of fine chemicals such as synthetic gas detergents, medicines and the like, and are widely applied. Hydrogen energy is a clean and efficient secondary energy and an important chemical raw material, has the characteristics of rich resources, wide sources, cleanness and high efficiency, and is known as the energy of 21 century.
The invention patent of China 'dechlorination method of waste plastic pyrolysis oil' discloses that waste plastic pyrolysis oil reacts with hydrogen under the action of a hydrogenation catalyst, hydrogenated product oil is obtained after oil-gas separation, and then the hydrogenated product oil is mixed with an adsorbent to obtain an oil product after the adsorption and dechlorination. The Chinese invention patent 'a waste plastic pyrolysis carbonization system' discloses the improvement of pyrolysis efficiency by crushing waste plastics and then incinerating the waste plastics for pyrolysis treatment. The Chinese invention patent 'an efficient waste plastic recycling granulator and granulating method' discloses a granulator table, a plasticizing device, a cooling device and a granule forming device, which simplifies the manufacturing process of waste plastic granules and reduces energy consumption. The invention discloses a sealed automatic feeding device and a method of a waste plastic pyrolysis treatment system, which comprises a pretreatment system, a liquefaction tank, a multi-stage liquid cyclone, a plastic pyrolysis system, a waste heat recovery system, a flue gas purification system, an oil-water separation system and the like. The invention discloses a method and a system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil, which are invented by China and disclose that absorption residual oil and desorption oil are obtained by carrying out absorption, desorption and separation on the waste plastic oil, and then products of the low-carbon olefin and the aromatic hydrocarbon are obtained by respectively carrying out catalytic cracking for multiple times.
The above patents relate to recycling processes of waste plastic granulation, pyrolysis carbonization, etc., but do not relate to further high-value utilization process of waste plastic, so that it is difficult to fundamentally improve the added value of the product, and in the recycling of waste plastic, it is often necessary to obtain a mixed product of low-carbon olefin and aromatic hydrocarbon by multiple cracking processes for waste plastic oil.
Disclosure of Invention
Aiming at the prior technical problems, the invention aims to provide a method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin comprises the following steps:
s1, pyrolysis and gasification: mixing the pretreated waste plastics with alkali lignin, and carrying out pyrolysis gasification at 190-1000 ℃ to generate a gas-phase product, a liquid-phase product and a solid-phase product;
s2, olefin preparation: adding a catalyst into the liquid-phase product in the step S1 to perform catalytic conversion at 300-1000 ℃ to obtain an olefin product; the catalyst component is selected from one or more of Si, O, ca, A, na, K or Cu;
s3, chemical chain reforming: in the step S1, the gas phase product and the oxygen carrier are subjected to chemical chain reforming at 800-1000 ℃; the active component of the oxygen carrier is selected from one or more of Fe, mn, co, ce, cu, ca, al, si or La;
s4, hydrogen preparation: reacting the oxygen carrier subjected to chemical chain reforming in the step S3 with steam at 700-1000 ℃ to obtain hydrogen;
s5, oxygen carrier regeneration: and (4) calcining the oxygen carrier reacted in the step (S4) in an air atmosphere at 800-1000 ℃, and performing a circulating reaction on the reacted oxygen carrier in the step (S3).
The invention couples alkali lignin with waste plastics, then carries out pyrolysis gasification, and utilizes alkali metals such as Na, al and the like in the alkali lignin to carry out pyrolysis gasification on the waste plastics to generate catalytic synergistic effect. Na, al and other alkali metals are reacted with Na 2 CO 3 /γ-Al 2 O 3 The catalyst has stronger decarboxylation and bond breaking effects and stronger selectivity to olefin and alkane, and the distribution and selectivity of liquid-phase products generated in the pyrolysis and gasification process of the waste plastic are further improved and enhanced under the catalysis of the catalyst, so that the technical problems of low yield of olefin products, low added value of products, low resource conversion rate and alkali metal treatment in the recycling of alkali lignin in the traditional waste plastic regeneration process are finally solved. The alkali lignin added in the invention generates a gas-phase product, a liquid-phase product and a solid-phase product after pyrolysis and gasification with the waste plastics, wherein the liquid-phase product can be used for preparing low-carbon olefin, the gas-phase product can be used for preparing high-purity hydrogen, and the solid-phase product is combusted by a combustor and is used for preparing high-purity hydrogenRecovering heat. The invention can not only cleanly and efficiently convert the waste plastic and the alkali lignin into the olefin and the high-purity hydrogen directly, but also co-produce the carbon black for combustion heat supply. After the treatment by the treatment process, the ash content of the product is less, and the product can be used for producing and bonding a binder for gas making of molded coal, a grinding aid for cement production, ceramics and refractory materials and the like.
The low-carbon olefin is a general name of olefin with 2-4 carbon atoms, namely small-molecular olefin such as ethylene, propylene, butylene and the like.
Specifically, the alkali lignin used in the present invention comprises: 43.99% of carbon, 0.29% of N and 4.77% of hydrogen.
Preferably, in the step S1, the reaction temperature of the pyrolysis gasification is 190 to 1000 ℃.
Further preferably, in the step S1, the reaction temperature of the pyrolysis gasification is 550 to 750 ℃.
Preferably, in the step S2, the catalytic conversion is performed at 500 to 600 ℃.
Specifically, in the step S2, the catalyst is a catalyst component conventionally used in the art.
Specifically, in the step S3, the oxygen carrier is an oxygen carrier component conventionally used in the art.
Preferably, the mass ratio of the alkali lignin to the pretreated waste plastic ranges from (0.10 to 0.99): 1. in the proportion range, the alkali lignin and the waste plastics have better catalytic synergistic effect. The inventors found through long-term studies that when the ratio of alkali lignin and waste plastic is lower than the above-mentioned mass ratio range, the catalytic synergistic effect thereof is not significant; when the ratio of the alkali lignin to the waste plastics exceeds the above mass ratio range, although the alkali lignin has a certain catalytic synergistic effect, the alkali lignin introduces excessive impurities, which affect the material fluidity and the selectivity of the olefin product in the pyrolysis and gasification process of the waste plastics, and the yield of the olefin is reduced.
Further preferably, the mass ratio of the alkali lignin to the pretreated waste plastic ranges from (0.60 to 0.99): 1.
preferably, the particle size of the alkali lignin is in the range of 40-200 meshes. The alkali lignin in the particle size range is easier to feed on one hand, and is convenient for heat and mass transfer to fully react in the reaction on the other hand.
Preferably, the particle size of the oxygen carrier is in the range of 20 to 80 mesh.
Preferably, in step S1, a gasifying agent is further added, and the gasifying agent is water vapor and/or air. The gasification agent can promote the conversion efficiency of the raw materials.
Preferably, in step S1, an inhibitor is further added, and the inhibitor is a Ca-based inhibitor. In particular calcium oxide. The inhibitor can inhibit the generation of chlorine-containing pollutants in the pyrolysis and gasification process of the waste plastics and reduce the formation of chlorine-containing precursors.
Preferably, in the step S1, the reaction time of the pyrolysis gasification is 0.5 to 10 hours.
Preferably, in the step S3, the reaction time of the chemical chain reforming is 10 to 40min.
Preferably, in the step S5, the oxygen carrier is calcined at 800 to 1000 ℃ for 60 to 80min in an air atmosphere.
Preferably, in the step S2, before the catalyst is added to the liquid-phase product, the liquid-phase product is further subjected to a refining process, wherein the refining process includes a denitrogenation refining process, a dechlorination refining process and a desilication refining process.
Preferably, in step S3, the gas-phase product is purified by spraying alkali solution, and then undergoes chemical-looping reforming with the oxygen carrier. The reformed tail gas obtained after the chemical chain reforming can be continuously combusted to supply heat for the system.
Preferably, the pretreatment comprises a pulverization treatment and/or a magnetic sorting treatment; the crushing treatment is to crush the waste plastics to obtain waste plastic particles with the particle size range of 5-50 mm; the magnetic separation treatment is to remove metal foreign matters in the waste plastics.
Further preferably, the method further comprises, before the pulverizing, subjecting the waste plastics to a drying process to reduce the water content of the waste plastics to 15% or less.
Preferably, in the step S1, the mixture of waste plastics and alkali lignin is conveyed to the gasification reactor by using a mechanical stirring and blanking device, so as to realize continuous blanking of the mixture. The mechanical stirring and blanking device is a lower rotary stirring type blanking device; set up water-cooling variable pitch spiral, realize the self sealss of material in transportation process, guarantee pyrolysis system oxygen content control.
In particular, the solid phase product is typically carbon black, which can be subsequently used for combustion heating, industrial boiler heating, or industrial fillers (e.g., as a filler in rubber).
Compared with the prior art, the invention has the following beneficial effects: the invention adopts waste plastic coupled alkali lignin for pyrolysis gasification, and utilizes alkali metals such as Na, al and the like in the alkali lignin to carry out pyrolysis gasification on the waste plastic to generate catalytic synergistic action, thereby solving the technical problems of low yield of olefin products, low added value of the products, low resource conversion rate and alkali metal treatment in the recycling of the alkali lignin in the traditional waste plastic regeneration process. The invention can cleanly and efficiently convert the waste plastic and the alkali lignin into the low-carbon olefin and the high-purity hydrogen, and can also co-produce the carbon black for combustion and heat supply. The method has the advantages of simple process, low cost and high added value of products.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
In addition, unless otherwise specified, reagents and materials used in the following examples are commercially available.
Example 1
A method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin comprises the following steps:
(1) And (3) crushing treatment: after impurities such as metal, glass, soil and the like are screened out from the waste plastics through preliminary sorting, drying treatment is carried out, and the water content of the waste plastics is reduced to below 15%; the dried waste plastics enter a crusher to be crushed into waste plastics particles with the particle size range of 5-15 mm;
(2) Magnetic separation treatment: waste plastic particles enter a conveyor belt, metal foreign matters in the waste plastic particles are screened and separated in a magnetic separation area, interference of the subsequent metal foreign matters on the waste plastic molding process is avoided, and equipment adopted in the magnetic separation process comprises a drum screen, a magnetic separator, a belt conveyor and the like;
(3) Pyrolysis and gasification: the waste plastic particles after magnetic separation treatment and alkali lignin with the particle size of 100 meshes are mixed according to the weight ratio of 0.02:1, entering a pyrolysis gasification process, and reacting for 3 hours at 500 ℃ to generate a gas-phase product, a liquid-phase product and a solid-phase product; in the pyrolysis gasification process, the waste plastics enter a gasification reactor through a stirring type blanking device to realize continuous blanking of the waste plastics, and meanwhile, a water-cooling variable-pitch screw is arranged in a screw feeder to realize self sealing of the materials in the conveying process; adding an inhibitor CaO;
(4) Olefin preparation: refining the liquid phase product by denitrogenation compound, chloride and silicide, entering into catalytic conversion stage, reacting at 450 deg.C for 30min under the action of catalyst to obtain olefin product and a small amount of liquid phase, and circulating and refluxing the small amount of liquid phase for reaction; the active component of the catalyst comprises Si/O/Ca/Al/Na;
(5) Chemical chain reforming: adopting a chemical precipitation method to construct a Fe/Co/Cu/Si-based composite oxygen carrier, calcining for 3 hours at 800-900 ℃, and crushing and screening to prepare oxygen carrier particles with the particle size range of 40-60 meshes; subjecting the gaseous products of pyrolysis gasification to Na-containing + After being sprayed and purified, the alkali liquor is subjected to chemical chain reforming with an oxygen carrier, a gas-phase product is contacted with the oxygen carrier at high temperature, the oxygen carrier is in a fixed state or a bubbling fluidized state, active components in the gas-phase product react with oxygen carrier lattice oxygen, the oxygen carrier is reduced into a low-valent oxide, the reaction temperature of the chemical chain reforming is 850 ℃, the reaction time is 30min, and reformed tail gas can be combusted to supply heat to a system;
(6) A hydrogen production process: reacting the oxygen carrier reacted in the step (5) with high-temperature water vapor at 800 ℃ for 25min to obtain high-purity hydrogen;
(7) Regeneration of oxygen carrier: regenerating the oxygen carrier reacted in the step (6) in a high-temperature air atmosphere at 900 ℃ and reacting for 60min; the reaction heat obtained in the regeneration process provides heat for the chemical looping reforming and hydrogen production processes through oxygen carrier circulation.
Results carried out, relative composition of the olefin products in step (4) as measured by Gas Chromatography (GC): c 2 ～C 4 Olefin content 32.39%, C 2 ～C 4 Alkane content 8.35%, C 5+ The content of the product was 2.11%, H 2 /CO/CO 2 /CH 4 The content of other gases is 56.17%; fuel conversion efficiency 61.17%. In the step (6), in the chemical looping hydrogen production process, the hydrogen yield is 0.85L/g, and H 2 The concentration was 89.11%.
Examples 2 to 9
The differences between examples 2 to 9 and example 1 are shown in table 1 below.
Comparative example 1
The differences between comparative example 1 and example 1 are shown in table 1 below.
TABLE 1
The test data for examples 1-5 and comparative example 1 are shown in table 2 below.
TABLE 2
As is clear from examples 1 to 5, the present invention utilizes waste plastics coupled with alkali lignin for pyrolysis gasification, and utilizes alkali metals such as Na and Al in the alkali lignin to generate catalytic synergistic effect on the pyrolysis gasification of the waste plastics. The yield of the finally prepared low-carbon olefin is between 32 and 66 percent; the fuel conversion efficiency was between 61 and 96%, and the yields of lower olefins and the fuel conversion efficiencies were also in this range in examples 6 to 10. Further, under the preparation conditions of examples 2 to 5, the yield of the finally prepared low-carbon olefin is between 55 and 66 percent; the fuel conversion efficiency is higher than 90%. Therefore, the method can cleanly and efficiently convert the waste plastics and the alkali lignin into the low-carbon olefin and the high-purity hydrogen directly, and can also co-produce carbon black for combustion and heat supply. The method has the advantages of simple process, low cost and high added value of products.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is conceivable, and the examples presented herein demonstrate the results of applicants' actual experiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where the claims recite a range of values, such ranges are intended to include all sub-ranges subsumed therein, and variations within the ranges are intended to be encompassed by the claims as appended hereto where possible.
Claims (10)
1. A method for preparing low-carbon olefin and co-producing high-purity hydrogen by coupling waste plastic with alkali lignin is characterized by comprising the following steps:
s1, pyrolysis and gasification: mixing the pretreated waste plastics with alkali lignin, and carrying out pyrolysis gasification at 190-1000 ℃ to generate a gas-phase product, a liquid-phase product and a solid-phase product;
s2, olefin preparation: adding a catalyst into the liquid-phase product in the step S1 to perform catalytic conversion at 300-1000 ℃ to obtain an olefin product; the catalyst component is selected from one or more of Si, O, ca, al, na, K, ni or Cu;
s3, chemical chain reforming: in the step S1, the gas phase product and the oxygen carrier are subjected to chemical chain reforming at 800-1000 ℃; the active component of the oxygen carrier is selected from one or more of Fe, mn, co, ce, cu, ca, al, si or La;
s4, hydrogen preparation: reacting the oxygen carrier subjected to chemical chain reforming in the step S3 with steam at 700-1000 ℃ to obtain hydrogen;
s5, oxygen carrier regeneration: and (4) calcining the oxygen carrier reacted in the step (S4) in an air atmosphere, and performing a circulating reaction on the calcined oxygen carrier in the step (S3).
2. The method according to claim 1, wherein the mass ratio of the alkali lignin to the pretreated waste plastic is in the range of (0.10 to 0.99): 1.
3. the method of claim 1, wherein the alkali lignin has a particle size in the range of 40 to 200 mesh.
4. The method of claim 1, wherein the oxygen carrier has a particle size in the range of 20 to 80 mesh.
5. The method according to claim 1, wherein in step S1, a gasifying agent is further added, and the gasifying agent is steam and/or air.
6. The method according to claim 1, wherein in step S1, an inhibitor is further added, wherein the inhibitor is a Ca-based inhibitor.
7. The method according to claim 1, wherein in step S1, the reaction time of the pyrolysis gasification is 0.5-10 h.
8. The method of claim 1, wherein in step S3, the reaction time of the chemical-looping reforming is 10 to 40min.
9. The method according to claim 1, wherein in step S2, the liquid-phase product is further subjected to a refining process before being added to the catalyst, the refining process including a denitrogenation refining process, a dechlorination refining process and a desilication refining process; and in the step S3, the gas-phase product is subjected to alkali liquor spraying purification and then is subjected to chemical chain reforming with the oxygen carrier.
10. The method according to claim 1, wherein the pretreatment comprises a pulverization treatment and/or a magnetic sorting treatment; the crushing treatment is to crush the waste plastics to obtain waste plastic particles with the particle size range of 5-50 mm; the magnetic separation treatment is to remove metal foreign matters in the waste plastics.
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| US20210155860A1 (en) * | 2019-11-25 | 2021-05-27 | Wormser Energy Solutions, Inc. | Char Preparation System and Gasifier for All-Steam Gasification with Carbon Capture |
| CN113979409A (en) * | 2021-11-05 | 2022-01-28 | 华中科技大学 | Organic solid waste treatment device and treatment method |
| CN114507541A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for preparing low-carbon olefin from waste plastic |
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| US20210155860A1 (en) * | 2019-11-25 | 2021-05-27 | Wormser Energy Solutions, Inc. | Char Preparation System and Gasifier for All-Steam Gasification with Carbon Capture |
| CN114507541A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for preparing low-carbon olefin from waste plastic |
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