CN112725003A - Method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol - Google Patents
Method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol Download PDFInfo
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- CN112725003A CN112725003A CN202011426472.5A CN202011426472A CN112725003A CN 112725003 A CN112725003 A CN 112725003A CN 202011426472 A CN202011426472 A CN 202011426472A CN 112725003 A CN112725003 A CN 112725003A
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol, which comprises the following steps: the ether-hydrocarbon mixed fuel is prepared by carrying out hydrogenation and etherification reactions on liquid product plastic crude oil obtained by pyrolyzing waste plastics and alcohol under the dual actions of heterogeneous catalysis and homogeneous catalysis, wherein the alcohol is mono-alcohol and/or polyalcohol. According to the method, an alcohol raw material and olefin in crude oil produced by waste plastics are directly subjected to etherification reaction, and the olefin in the crude oil is converted into saturated hydrocarbon through normal-pressure hydrogenation, so that the ether-hydrocarbon mixed fuel is obtained.
Description
Technical Field
The invention belongs to the technical field of fuel production by wastes, and particularly relates to a method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol.
Background
In the production process of production enterprises in the recycled paper industry and the like in China, a large amount of solid pollutants mainly comprising waste plastics are generated, and most of the solid pollutants cannot be used as recycled plastic raw materials and can only be treated as wastes. The wastes can not be used as garbage for landfill to cause white pollution, and can not be simply put into a common tin furnace to be combusted to generate dioxin. In this regard, how to process waste plastics in the recycled paper industry becomes a bottleneck for the survival and development of enterprises, so that social attention is extremely high.
The conventional waste plastic treatment method is roughly as follows: 1. the waste is incinerated, but the air pollution is caused; 2. landfill and natural degradation are carried out, but water pollution and soil pollution can be caused; 3. the fuel oil is simply cracked into low-quality fuel oil to enter the market, but the pollution in the production process is serious, the product quality is poor, secondary pollution is caused in the recycling process of the market, and the fuel oil is strictly forbidden by the state and basically disappears at present. 4. By taking the waste oil and waste solid (organic) treatment technology as a reference, the most effective method is high-pressure hydrogenation at present, but the high-pressure hydrogenation is taken as a world problem at present, the treatment process has multiple factors, and plastics are easy to coke in the pyrolysis process, so that the high-pressure hydrogenation technology is difficult to be applied to the treatment of the waste plastics in paper plants.
Chinese patent document CN108517222A discloses a continuous production process for preparing high-purity combustible gas from waste plastics of a recycled paper plant, which comprises pyrolyzing waste plastics to generate water and generate combustible mixed gas, then repeatedly pyrolyzing crude plastic oil into combustible gas by secondary pyrolysis, and performing multi-stage cooling separation and purification treatment.
Chinese patent document CN105479621A discloses a method for recycling waste plastics of paper mill, which comprises subjecting the obtained polyolefin plastics to lime emulsion treatment, then to solvent reprocessing step, and separating and purifying the treated polyolefin plastics. The method adopts large amount of organic solvent, has complex post-treatment process, generates a large amount of organic waste liquid, and cannot realize clean production.
On the other hand, the existing catalytic cracking process has the characteristic of gradual endothermic liquefaction due to poor thermal conductivity of the plastic, the liquefied plastic can still become solid instead of monomer once being separated from the hot environment, and the monomer formation of the plastic requires a long time, so that the yield of the catalytic cracking process liquid is very low; meanwhile, the plastic is easy to dehydrogenate and carbonize under high-temperature cracking to generate condensation reaction, the content of saturated hydrocarbon in the obtained liquid oil product is low, the oxidation resistance is poor, the fuel oil obtained by high-temperature cracking of the waste plastic has extremely low quality, soluble colloid is easy to generate, and the fuel oil is accompanied by blackening phenomenon and peculiar smell and is difficult to carry out post-treatment.
The scheme of generating a large amount of fusel in the existing industrial treatment scheme, how to fully utilize the fusel for resource treatment and how to use crude oil obtained from waste plastics for producing ether hydrocarbon fuel becomes a technical problem to be solved urgently.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing an ethereal hydrocarbon fuel from waste plastics and waste alcohols. According to the method, an alcohol raw material and olefin in crude oil produced by waste plastics are directly subjected to etherification reaction, and the olefin in the crude oil is converted into saturated hydrocarbon through normal-pressure hydrogenation to obtain the ether-hydrocarbon mixed fuel.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for producing ether hydrocarbon fuel from waste plastic and waste alcohol, comprising the steps of:
(1) pyrolyzing the waste plastics at the reaction temperature of 250-300 ℃, under the reaction pressure of-0.4-0.8 MPa and under the nitrogen atmosphere oxygen-free environment to obtain a liquid product, namely plastic crude oil;
(2) selecting fusel as a raw material, wherein the alcohol is mono-alcohol and/or polyalcohol;
(3) carrying out etherification and hydrogenation reactions on the plastic crude oil obtained in the step (1) and the alcohol obtained in the step (2) under alcohol-adding homogeneous catalysis and hydrogenation heterogeneous catalysis to obtain ether-hydrocarbon mixed fuel;
wherein the heterogeneous catalyst is: 3 parts of cerium dioxide, 3 parts of titanium dioxide, 1 part of zirconia, 5 parts of zeolite and 5 parts of carbon fiber; the homogeneous catalyst is: wilkinson catalystReagent RhCl (pph)3)35 parts of potassium hydroxide, 3 parts of potassium hydroxide and 3 parts of magnesium hydroxide.
Further, the alcohol in the step (2) includes at least one of methanol, ethanol, ethylene glycol, n-propanol, isobutanol, isoamyl alcohol, active amyl alcohol or phenylethyl alcohol.
Further, the reaction temperature in the step (3) is 350-400 ℃, and the reaction time is 10-20 s. The reaction is extremely fast due to the catalytic promotion effect of the catalyst.
Further, the weight ratio of the plastic crude oil to the alcohol in the step (3) is 100: 2-5.
Further, the amount of the catalyst used in the step (3) is 0.2-0.5% of the total weight of the plastic crude oil and the alcohol.
The invention has the following beneficial effects:
(1) the invention provides a method for obtaining ether hydrocarbon mixed fuel by adopting crude oil produced by alcohol raw materials and waste plastics, and provides a new fuel capable of replacing petrochemical resources;
(2) the ether hydrocarbon mixed fuel obtained by the method has excellent effect as power fuel and kitchen fuel, has low emission, and can be used as clean fuel for replacing petrochemical resources.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is described in detail below with reference to the following embodiments, and it should be noted that the following embodiments are only for explaining and illustrating the present invention and are not intended to limit the present invention. The invention is not limited to the embodiments described above, but rather, may be modified within the scope of the invention.
The preparation method of the plastic crude oil in the following examples is as follows:
after removing heavy metals from the waste plastics, carrying out pyrolysis reaction on the waste plastics at 250-300 ℃ and-0.4-0.8 MPa (nitrogen atmosphere) in an oxygen-free environment in nitrogen atmosphere to obtain a liquid product.
The catalyst comprises the following components in parts by weight:
heterogeneous catalyst: 3 parts of cerium dioxide, 3 parts of titanium dioxide, 1 part of zirconia, 5 parts of zeolite and 5 parts of carbon fiber;
homogeneous catalyst: wilkinson's catalyst RhCl (pph)3)3(triphenylphosphine rhodium chloride, manufactured by Shanghai Tuo Si chemical Co., Ltd.) 5 parts, potassium hydroxide 3 parts, and magnesium hydroxide 3 parts.
Example 1
Mixing the plastic crude oil and mixed alcohol according to a mass ratio of 100:2, and sequentially carrying out alcohol-adding homogeneous catalysis and hydrogenation heterogeneous catalysis reaction (normal-pressure hydrogenation) under the action of a catalyst, wherein the dosage of the catalyst is 0.5 percent of the total weight of the plastic crude oil and the mixed alcohol, the reaction temperature is 350 ℃, and the reaction time is 10s, so as to obtain the ether hydrocarbon mixed fuel, wherein the mixed alcohol is a mixture of n-propanol and isobutanol according to a mass ratio of 1: 1.
Example 2
Mixing the plastic crude oil and alcohol according to a mass ratio of 100:5, and sequentially carrying out alcohol-adding homogeneous catalysis and hydrogenation heterogeneous catalysis reaction (normal-pressure hydrogenation) under the action of a catalyst, wherein the dosage of the catalyst is 0.2 percent of the total weight of the plastic crude oil and the alcohol, the temperature of etherification is 400 ℃, and the reaction time is 20s, so as to obtain the ether hydrocarbon mixed fuel, wherein the alcohol is n-propanol.
Comparative example 1
The process of example 1 is followed, wherein the components titanium dioxide 3 parts and carbon fibers 5 parts are removed from the heterogeneous catalyst.
Comparative example 2
The procedure of example 1 was followed, wherein 3 parts of potassium hydroxide as a component in the homogeneous catalyst was removed, and Wilkinson's catalyst RhCl (pph)3)3The mixture is adjusted to 8 portions.
Comparative example 3
The process of example 1 is followed, wherein the proportions of the components in the catalyst are adjusted to: heterogeneous catalyst: 3 parts of magnesium oxide, 3 parts of cerium dioxide, 3 parts of zirconium oxide and 6 parts of zeolite; homogeneous catalyst: wilkinson's catalyst RhCl (pph)3)35 parts of sodium hydroxide and 5 parts of sodium hydroxide.
Test example 1
The unsaturated hydrocarbon content in the ether hydrocarbon mixed fuels obtained in examples 1 to 2 and comparative examples 1 to 3 was measured, and the results showed that: no unsaturated hydrocarbon was detected in examples 1 to 3, while the content of unsaturated hydrocarbon detected in comparative examples 1 to 3 was still 5 to 10%, indicating that the etherification reaction was not complete.
Test example 2
The ether-hydrocarbon mixed fuels obtained in examples 1 to 2 and comparative examples 1 to 3 were added to a diesel engine for combustion test, and compared with national standard 0#And (3) comparing the diesel oil, selecting a DK4A type diesel engine for scientific research to perform a bench test, testing the emission performance of the engine at 2400r/min load characteristics corresponding to working points, and showing the emission result in table 1.
TABLE 1
Note: in the table, the "-" symbol before each numerical value is shown as being equal to national standard 0#The diesel emission is reduced by a proportion of the reduction in the diesel emission.
Claims (6)
1. A method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol is characterized by comprising the following steps:
(1) pyrolyzing the waste plastics at the reaction temperature of 250-300 ℃, under the reaction pressure of-0.4-0.8 MPa and under the nitrogen atmosphere oxygen-free environment to obtain a liquid product, namely plastic crude oil;
(2) selecting alcohol as a raw material, wherein the alcohol is mono-alcohol and/or polyalcohol;
(3) carrying out etherification and hydrogenation reactions on the plastic crude oil obtained in the step (1) and the alcohol raw material obtained in the step (2) under alcohol-adding homogeneous catalysis and hydrogenation heterogeneous catalysis to obtain an ether-hydrocarbon mixed fuel;
the catalyst components for the alcohol-adding homogeneous catalytic reaction and the hydrogenation heterogeneous catalytic reaction are as follows in parts by weight:
the heterogeneous catalyst is: 3 parts of cerium dioxide, 3 parts of titanium dioxide, 1 part of zirconia, 5 parts of zeolite and 5 parts of carbon fiber;
the homogeneous catalyst is: wilkinson catalysisAgent RhCl (pph)3)35 parts of potassium hydroxide, 3 parts of potassium hydroxide and 3 parts of magnesium hydroxide.
2. The method for producing ether hydrocarbon fuel from waste plastics and waste alcohols according to claim 1, wherein the alcohol in step (2) comprises at least one of methanol, ethanol, ethylene glycol, n-propanol, isobutanol, isoamyl alcohol, active amyl alcohol or phenylethyl alcohol.
3. The method for producing ether hydrocarbon fuel from waste plastics and waste alcohols according to claim 1, wherein the reaction sequence in step (3) is to perform the alcohol-adding homogeneous catalytic reaction first and then the hydrogenation heterogeneous catalytic reaction.
4. The method for producing an ethereal hydrocarbon fuel from waste plastics and waste alcohols according to claim 1, wherein the temperature of the reaction in step (3) is 350 to 400 ℃ and the reaction time is 10 to 20 s.
5. The method for producing ether hydrocarbon fuel from waste plastics and waste alcohol according to claim 1, wherein the weight ratio of the plastic crude oil to the alcohol in step (3) is 100: 2-5.
6. The method for producing ether hydrocarbon fuel from waste plastics and waste alcohol according to claim 5, wherein the amount of the catalyst used in step (3) is 0.2-0.5% of the total weight of the plastic crude oil and the alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011426472.5A CN112725003A (en) | 2020-12-09 | 2020-12-09 | Method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol |
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| CN202011426472.5A CN112725003A (en) | 2020-12-09 | 2020-12-09 | Method for producing ether hydrocarbon fuel by using waste plastics and waste alcohol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114164022A (en) * | 2021-11-24 | 2022-03-11 | 成都前成科技有限公司 | Etherification and solvent refining process of plastic reclaimed oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106180136A (en) * | 2016-07-12 | 2016-12-07 | 环境保护部华南环境科学研究所 | A kind of solid waste recovery processing technique |
| CN107309243A (en) * | 2017-06-21 | 2017-11-03 | 河南地之绿环保科技有限公司 | A kind of processing method of plastic garbage |
-
2020
- 2020-12-09 CN CN202011426472.5A patent/CN112725003A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106180136A (en) * | 2016-07-12 | 2016-12-07 | 环境保护部华南环境科学研究所 | A kind of solid waste recovery processing technique |
| CN107309243A (en) * | 2017-06-21 | 2017-11-03 | 河南地之绿环保科技有限公司 | A kind of processing method of plastic garbage |
Non-Patent Citations (1)
| Title |
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| 宁正新: "《青少年科普丛书 多姿物理》", 30 April 2012, 北京联合出版公司 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114164022A (en) * | 2021-11-24 | 2022-03-11 | 成都前成科技有限公司 | Etherification and solvent refining process of plastic reclaimed oil |
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Application publication date: 20210430 |