CN114164022B - Etherification and solvent refining process for plastic reclaimed oil - Google Patents
Etherification and solvent refining process for plastic reclaimed oil Download PDFInfo
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- CN114164022B CN114164022B CN202111403500.6A CN202111403500A CN114164022B CN 114164022 B CN114164022 B CN 114164022B CN 202111403500 A CN202111403500 A CN 202111403500A CN 114164022 B CN114164022 B CN 114164022B
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- reclaimed oil
- plastic reclaimed
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
- C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides an etherification and solvent refining process of plastic reclaimed oil, belonging to the refining processing technology of plastic reclaimed oil. The process provided by the invention comprises the following steps: (1) Carrying out homogeneous catalysis oxygenation etherification on the plastic reclaimed oil and small molecular alcohol at 350-400 ℃ under normal pressure to obtain etherified plastic reclaimed oil; (2) And (3) refining the etherified plastic reclaimed oil by using a solvent to obtain the refined ether hydrocarbon fuel. The process provided by the invention is used for carrying out etherification on the plastic reclaimed oil and then carrying out solvent refining treatment, so that the process can be effectively applied to refining of the plastic reclaimed oil, and the yield and quality of the ether hydrocarbon fuel oil can be greatly improved. In addition, when the diethylene glycol dimethyl ether and the polymethoxy dimethyl ether are mixed according to the mass ratio of 5-2:1, the invention has the advantages of low emission, little pollution, low toxicity of the used solvent, no need of complete separation and treatment cost saving.
Description
Technical Field
The invention belongs to a refining processing technology of plastic reclaimed oil, and particularly relates to an etherification and solvent refining technology of plastic reclaimed oil.
Background
The waste plastics in China have large output, and particularly, a large amount of low-value plastics with complex components and difficult physical regeneration cannot be properly treated, and the treatment modes of the waste plastics are as follows: 1. waste incineration, but atmospheric pollution is caused; 2. landfill and natural degradation, but can cause water pollution and soil pollution; 3. cracking into low-quality fuel oil enters the market, but the pollution in the production process is large, and the quality of the product is poor. The national authorities have clearly indicated that such low quality fuel oils do not meet quality standards and still need to be listed in the hazardous waste management directory.
At present, the most effective method at home and abroad is to completely crack waste plastics to be converted into plastic reclaimed oil under proper conditions after cracking and then refine the plastic reclaimed oil by high-pressure hydrogenation. However, as a world problem, the technology content is high, and a plurality of constraint factors exist in the treatment process, such as coking phenomenon of plastics in the cracking process, complex products, large investment and high equipment operation cost. Therefore, the technology is difficult to popularize in the field of low-value waste plastic treatment of waste plastics in a recycled paper mill, agricultural films and the like.
Solvent refining is a simple and effective oil quality improvement mode, the prior art has a method for treating waste lubricating oil by adopting solvent refining, and common solvents include furfural, N-methylpyrrolidone (NMP), phenol and the like. A great deal of research work is carried out by the scholars of China aiming at the waste plastic thermal/cracking process, and the research indicates that the plastic reclaimed oil with high impurity content is obtained in the first step no matter the pyrolysis process or the cracking process, and the high-quality fuel oil meeting the national standard can be obtained only by further refining the plastic reclaimed oil. The plastic reclaimed oil generated by pyrolysis or pyrolysis generally contains more cycloparaffin, aromatic hydrocarbon and other macromolecular substances, when the plastic reclaimed oil is directly treated by adopting a solvent refining mode, the plastic reclaimed oil cannot be effectively separated, and impurities in the solvent and the plastic reclaimed oil cannot reach an ideal layering state, so that the solvent refining effect is not ideal, and the oil yield is finally influenced. How to treat the plastic reclaimed oil by means of the existing solvent refining method of the waste lubricating oil so as to solve the problems of no delamination, low oil yield and the like is a key technical problem to be solved urgently at the present stage.
In addition, furfural, N-methylpyrrolidone (NMP), phenol and the like widely used at the present stage belong to organic solvents, have high toxicity and have certain environmental hidden trouble. How to develop safe, environment-friendly and efficient refining solvent, and further improve the oil yield on the premise of ensuring the quality of the refined fuel oil, is another key technical problem to be solved urgently in the field.
Disclosure of Invention
Based on the key technical problems, the invention provides an etherification and solvent refining process of plastic reclaimed oil. According to the invention, the plastic reclaimed oil is subjected to etherification and then is subjected to solvent refining treatment, so that the linear alkane in the plastic reclaimed oil is increased, the duty ratio of naphthene and aromatic hydrocarbon is reduced, the solvent refining effect is improved, the toxicity of the used solvent is low, and the solvent can be used as a component in an oil product without complete separation and is used for combustion application of fuel oil.
In order to achieve the above object, the process method adopted by the invention comprises the following steps:
(1) Carrying out homogeneous catalysis oxygenation etherification on plastic reclaimed oil obtained by pyrolysis or pyrolysis of waste plastics, wherein the etherification operation is as follows: carrying out homogeneous catalysis reaction with small molecular alcohol at 350-400 ℃ under normal pressure to obtain etherified plastic reclaimed oil;
(2) And (3) carrying out solvent refining on the plastic reclaimed oil after etherification in the step (1) to obtain the refined ether hydrocarbon fuel.
The applicant treats waste plastic reclaimed oil by an etherification and oxygenation method, specifically, the etherified plastic reclaimed oil is obtained firstly by homogeneous catalysis, and then the etherified plastic reclaimed oil is treated by a solvent refining process, so that the solvent refining effect is greatly improved, and the oil yield and quality are also greatly improved. The principle is that after the etherification technology is adopted, the linear alkane in the plastic reclaimed oil is increased, and the content ratio of naphthene and aromatic hydrocarbon is reduced, so that the solvent refining effect is obviously improved; when the etherification process is not adopted, the plastic reclaimed oil is directly treated by adopting the traditional solvent refining method, and the plastic reclaimed oil is found to be unable to be well layered with the solvent, and the obtained oil yield is low, which indicates the advantages of the invention compared with the traditional solvent refining method. Therefore, the invention carries out the traditional solvent refining process after etherification treatment, and is the key for ensuring that the plastic reclaimed oil can be refined to obtain high-quality ether hydrocarbon fuel.
Particularly, the invention provides a method for refining and processing plastic reclaimed oil by adopting diethylene glycol dimethyl ether and polymethoxy dimethyl ether as mixed solvents according to a mass ratio of 5-2:1 on the basis of a traditional solvent refining method. Compared with the traditional solvent refining method, the method has the advantages that the toxicity of the used solvent is lower, complete separation is not needed, the mixed solvent is dissolved in the etherified plastic reclaimed oil and can be directly used as fuel oil, and the combustion quality of the fuel oil after the plastic reclaimed oil is refined is greatly improved.
Further, the mass ratio of the etherified plastic reclaimed oil to the solvent is 60-70:30-40. The solvent can be a traditional solvent (furfural, N-methylpyrrolidone and phenol) or a mixed solvent provided by the invention.
Further, the catalyst for homogeneous catalysis reaction in the step (1) comprises the following components in parts by weight: 5 parts of wilkinson catalyst, 3 parts of potassium hydroxide and 3 parts of magnesium hydroxide.
Further, the catalyst in the step (1) is used in an amount of 0.1 to 0.3 percent of the weight of the plastic reclaimed oil.
Further, the reaction time of the homogeneous catalytic reaction is 10 to 20 seconds.
Further, in the step (1), the mass ratio of the small molecular alcohol to the plastic reclaimed oil is 1-3:100. The small molecule alcohol comprises pure/abandoned methanol, ethanol or propanol. The waste methanol, ethanol or propanol herein means that the purity of methanol, ethanol or propanol does not need to reach 100%, but generally only needs to reach 60% or more.
Further, in the step (2), the polymethoxy dimethyl ether is DMM n ，n＝3～8。
Further, in the step (2), solvent refining equipment is adopted, and different components are separated through reduced pressure distillation of mixed oil, so that refined ether hydrocarbon fuel is obtained.
The beneficial effects of the invention are as follows:
the invention provides a treatment method for refining plastic reclaimed oil by solvent after etherification, and the ether hydrocarbon fuel obtained by the treatment has high quality, can be directly used as fuel oil, and has small emission and small environmental pollution. Particularly, the mixed solvent selected by the invention well solves the problems of high solvent toxicity and complex post-treatment in the existing solvent refining process, does not need to be completely removed from the waste reclaimed oil, greatly simplifies the solvent refining treatment step and saves the cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be specifically described below with reference to examples. The following examples are given for the purpose of illustration and description only and are not intended to be limiting. Some non-essential modifications and adaptations of the invention according to the foregoing summary will still fall within the scope of the invention.
Example 1
An etherification and solvent refining process of plastic reclaimed oil comprises the following steps:
(1) Adding plastic reclaimed oil (obtained by cracking waste plastic) into a normal pressure reaction kettle, adding waste methanol (the content is 80 percent, v/v) according to 1 percent of the weight of the plastic reclaimed oil, fully stirring and mixing, adding a catalyst (the catalyst comprises 5 parts by weight of Wilkinson catalyst, 3 parts by weight of potassium hydroxide and 3 parts by weight of magnesium hydroxide, the catalyst consumption is 0.1 percent of the weight of the plastic reclaimed oil), and carrying out homogeneous catalytic reaction at the normal pressure at 350 ℃ for 10 seconds to obtain etherified plastic reclaimed oil;
(2) And (3) carrying out solvent refining on the etherified plastic reclaimed oil in the step (1) by adopting solvent refining equipment, wherein the solvent adopted in the solvent refining is furfural, the mass ratio of the etherified plastic reclaimed oil to the furfural is 60:40, the mixed oil is evaporated, and different components are separated to obtain the refined ether hydrocarbon fuel.
Example 2
An etherification and solvent refining process of plastic reclaimed oil comprises the following steps:
(1) Adding plastic reclaimed oil (obtained by pyrolyzing waste plastic) into a normal pressure reaction kettle, adding waste methanol (content 65%, v/v) according to 2% of the weight of the plastic reclaimed oil, fully stirring and mixing, adding a catalyst (the catalyst comprises 5 parts by weight of Wilkinson catalyst, 3 parts by weight of potassium hydroxide and 3 parts by weight of magnesium hydroxide, and the catalyst consumption is 0.2% of the weight of the plastic reclaimed oil), carrying out homogeneous catalytic reaction at 380 ℃ under normal pressure for 20s, and obtaining etherified plastic reclaimed oil;
(2) Carrying out solvent refining on the etherified plastic reclaimed oil in the step (1) by adopting solvent refining equipment, evaporating mixed oil, and separating different components to obtain refined ether hydrocarbon fuel, wherein the solvents adopted in the solvent refining are diethylene glycol dimethyl ether and polymethoxy dimethyl ether (DMM) n N=3 to 6) according to the mass ratio of 5:1, the mass ratio of the etherified plastic reclaimed oil to the mixed solvent is 70:30.
Example 3
An etherification and solvent refining process of plastic reclaimed oil comprises the following steps:
(1) Adding plastic reclaimed oil (obtained by cracking waste plastic) into a normal pressure reaction kettle, adding methanol (the content of which is 90 percent, v/v) according to 3 percent of the weight of the plastic reclaimed oil, fully stirring and mixing, adding a catalyst (the catalyst comprises 5 parts by weight of Wilkinson catalyst, 3 parts by weight of potassium hydroxide and 3 parts by weight of magnesium hydroxide, and the catalyst consumption is 0.3 percent of the weight of the plastic reclaimed oil), carrying out homogeneous catalytic reaction at 400 ℃ under normal pressure for 15 seconds, and obtaining etherified plastic reclaimed oil;
(2) Carrying out solvent refining on the etherified plastic reclaimed oil in the step (1) by adopting solvent refining equipment, evaporating mixed oil, and separating different components to obtain refined ether hydrocarbon fuel, wherein the solvents adopted in the solvent refining are diethylene glycol dimethyl ether and polymethoxy dimethyl ether (DMM) n N=3 to 8) according to the mass ratio of the mixture of 2:1, the mass ratio of the etherified plastic reclaimed oil to the mixed solvent of 60:40.
Comparative example 1
According to the method of example 1, the etherification operation of step (1) is removed, and the solvent refining operation of step (2) is directly performed on the plastic reclaimed oil, so that the plastic reclaimed oil and the solvent are not layered, the solvent refining effect is poor, the refined oil yield is below 20%, and a large amount of high-quality fuel oil cannot be obtained.
Comparative example 2
According to the method of example 2, solvent furfural is selected in step (2) for solvent refining operation, multi-step heat exchange evaporation and stripping dissolution recovery treatment are required for furfural, the recovery treatment efficiency is low, and the quality of the obtained ether hydrocarbon fuel is low through combustion test.
Comparative example 3
According to the method of example 3, solvent N-methylpyrrolidone (NMP) is selected in step (2) for solvent refining operation, multi-step heat exchange evaporation and stripping dissolution recovery treatment are required for NMP, the recovery treatment efficiency is low, and the quality of the obtained ether hydrocarbon fuel is not high through the test of combustion.
Experimental example
The ether hydrocarbon fuels obtained in examples 1-3 and comparative examples 1-3 were subjected to an engine emission test, DK4A type diesel engines for scientific research were selected for bench test, and the emission performance of the ether hydrocarbon fuels at the operating point of the engine corresponding to 2400r/min load characteristics was tested, and was tested by national standard 0 # Diesel is used as a reference object, and is calculated and standardized with national standard 0 according to the method of national standard of' GB19147-2016 diesel for vehicles # The emission amount of diesel oil is increased and decreased by the national standard 0 # The amount of diesel fuel discharged was reduced in negative sign and increased in positive sign), and the results are shown in table 1.
TABLE 1
Claims (8)
1. The etherification and solvent refining process of the plastic reclaimed oil is characterized by comprising the following steps of:
(1) Carrying out homogeneous catalysis oxygenation etherification on plastic reclaimed oil obtained by pyrolysis or pyrolysis of waste plastics, wherein the etherification operation is as follows: carrying out homogeneous catalysis reaction with small molecular alcohol at 350-400 ℃ under normal pressure to obtain etherified plastic reclaimed oil;
(2) Carrying out solvent refining on the etherified plastic reclaimed oil in the step (1) to obtain refined ether hydrocarbon fuel;
wherein the solvent adopted in the solvent refining is a mixture of diethylene glycol dimethyl ether and polymethoxy dimethyl ether according to a mass ratio of 5-2:1; the mass ratio of the etherified plastic reclaimed oil to the solvent is 60-70:30-40.
2. The etherification and solvent refining process of plastic reclaimed oil according to claim 1, wherein the catalyst of the homogeneous catalytic reaction in step (1) comprises, in parts by weight: 5 parts of wilkinson catalyst, 3 parts of potassium hydroxide and 3 parts of magnesium hydroxide.
3. The process for etherification and solvent refining of plastic reclaimed oil according to claim 1, wherein the catalyst in step (1) is used in an amount of 0.1 to 0.3% by weight based on the weight of the plastic reclaimed oil.
4. The process for etherification and solvent refining of plastic reclaimed oil according to claim 1, wherein the reaction time of the homogeneous catalytic reaction in step (1) is 10 to 20s.
5. The process for etherification and solvent refining of plastic reclaimed oil according to claim 1, wherein the mass ratio of the small molecular alcohol to the plastic reclaimed oil in the step (1) is 1-3:100.
6. The process for etherification and solvent refining of a plastic reclaimed oil of claim 1 wherein the small molecule alcohol of step (1) comprises pure/waste methanol, ethanol or propanol.
7. The process for etherification and solvent refining of a plastic reclaimed oil according to claim 1, wherein the polymethoxy dimethyl ether in step (2) is DMM n ，n＝3～8。
8. The process for etherification and solvent refining of plastic reclaimed oil according to claim 1, wherein in the step (2), a solvent refining device is adopted, and different components are separated through vacuum rectification of the mixed oil, so as to obtain the refined ether hydrocarbon fuel.
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| CN108587765A (en) * | 2018-06-06 | 2018-09-28 | 武汉科林精细化工有限公司 | A kind of pretreating process of the high-quality base oil of waste lubricant oil regeneration |
| CN110724563A (en) * | 2019-08-30 | 2020-01-24 | 浙江工业大学 | Method for regenerating waste engine oil by combining solvent extraction and extraction centrifugation |
| CN112725016A (en) * | 2020-12-09 | 2021-04-30 | 成都前成科技有限公司 | Production method for normal-pressure hydrofining waste plastic oil |
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| CN1092096A (en) * | 1993-12-30 | 1994-09-14 | 姜皓 | Utilize the method and apparatus of waste or used plastics extracting gasoline, diesel oil distillate and liquefied gas |
| CN1127554C (en) * | 2000-07-12 | 2003-11-12 | 北京乐意环保技术有限公司 | Technological process and equipment of utilizing waste plastics to product gasoline, desel oil and liquiefied gas |
| CN1250677C (en) * | 2004-08-06 | 2006-04-12 | 姜皓 | Waste plastic oiling device for continuous industrial production at large scale |
| CN112725012A (en) * | 2020-12-09 | 2021-04-30 | 成都前成科技有限公司 | Production method of etherified oxygenated deep-processing waste plastic oil |
| CN112725003A (en) * | 2020-12-09 | 2021-04-30 | 成都前成科技有限公司 | Method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108587765A (en) * | 2018-06-06 | 2018-09-28 | 武汉科林精细化工有限公司 | A kind of pretreating process of the high-quality base oil of waste lubricant oil regeneration |
| CN110724563A (en) * | 2019-08-30 | 2020-01-24 | 浙江工业大学 | Method for regenerating waste engine oil by combining solvent extraction and extraction centrifugation |
| CN112725016A (en) * | 2020-12-09 | 2021-04-30 | 成都前成科技有限公司 | Production method for normal-pressure hydrofining waste plastic oil |
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