阅读说明：本技术 一种醚化加氧深加工废弃塑料油的生产方法 (Production method of etherified oxygenated deep-processing waste plastic oil ) 是由 刘锦超 陈天晓 邓子林 宋君祥 于 2020-12-09 设计创作，主要内容包括：本发明提供了一种醚化加氧深加工废弃塑料油的生产方法,所述生产方法包括如下步骤：以废弃塑料经过热解后所得废弃塑料油为原料,在1个大气压和350～400℃的温度条件下,以所述废弃塑料油的重量百分比计,加入1～3％的甲醇和0.1～0.3％催化剂,进行均相催化,反应完全后,即得醚化后的醚烃燃料；所述催化剂按重量份计由如下组分组成：威尔金森催化剂RhCl(pph-3)-35份、复合碱6份。本发明能在常压环境下对废弃塑料油进行醚化加氧,从而获得排放量低的醚烃燃料,解决了现有技术中存在的工艺条件苛刻、产物难具有实际工业应用价值的缺点,具有良好的市场前景。(The invention provides a production method of etherified oxygenated deep-processing waste plastic oil, which comprises the following steps: taking waste plastic oil obtained after pyrolysis of waste plastics as a raw material, adding 1-3% of methanol and 0.1-0.3% of a catalyst by weight percentage of the waste plastic oil under the conditions of 1 atmospheric pressure and 350-400 ℃, performing homogeneous catalysis, and obtaining etherified ether hydrocarbon fuel after complete reaction; the catalyst comprises the following components in parts by weight: wilkinson's catalyst RhCl (pph) 3 ) 3 5 parts of composite alkali and 6 parts of composite alkali. The invention can carry out etherification and oxygenation on the waste plastic oil under the normal pressure environment, thereby obtaining ether hydrocarbon fuel with low emission, solving the defects of harsh process conditions and difficult product having practical industrial application value in the prior art and having good market prospect.)

1. The production method of the etherified oxygenated deep processing waste plastic oil is characterized by comprising the following steps:

taking waste plastic oil obtained by pyrolyzing waste plastics as a raw material, adding 1-3 wt% of methanol and a small amount of catalyst into the waste plastic oil according to the weight percentage of the waste plastic oil under the conditions of 1 atmospheric pressure and 350-400 ℃, and carrying out homogeneous catalytic reaction to obtain oxygenated ether hydrocarbon fuel;

the catalyst comprises the following components in parts by weight:

wilkinson's catalyst RhCl (pph)₃)₃5 parts of composite alkali and 6 parts of composite alkali; wherein the composition of the composite alkali is as follows: 3 parts of potassium hydroxide and 3 parts of magnesium hydroxide。

2. The production method according to claim 1, wherein the amount of the catalyst added is 0.1 to 0.3% of the total amount of the waste plastic oil.

3. The production method according to claim 1, wherein the purity of the methanol is 99.0% or more.

4. The production method according to claim 1, wherein the reaction time of the homogeneous catalytic reaction is 10 to 20 seconds.

5. The production method according to claim 1, wherein the waste plastic oil is obtained by: after heavy metals in the waste plastic are removed, condensing the vapor-liquid mixture at 250-300 ℃ and-0.4-0.8 MPa in an oxygen-free environment to obtain the composite material.

Technical Field

The invention belongs to the field of deep processing of waste plastics, relates to a preparation technology of clean gasoline, and particularly relates to a production method of etherified oxygenated deep processing waste plastic oil.

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 at present is high-pressure hydrogenation, waste plastics are completely decomposed and converted into hydrocarbon oil under the conditions of high temperature and high pressure, but the method is taken as a world problem at present, the technical components are high, multiple factors exist in the treatment process, and the plastic is easy to coke in the pyrolysis process, so that the high-pressure hydrogenation technology is difficult to popularize in the treatment of waste plastics in paper factories in a large range.

Chinese patent document CN 108517222 a 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 CN 105479621 a 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.

Therefore, how to upgrade the quality of the crude oil generated from the waste plastics under normal pressure becomes a technical problem to be solved urgently.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a method for etherifying plastic oil obtained by pyrolyzing waste plastics under normal pressure to obtain ether hydrocarbon fuel, and the method is used for achieving the purpose and solving the defects that the corresponding reaction is difficult to be carried out under the normal pressure and the emission reduction effect of the obtained fuel oil is poor in the prior art.

In order to achieve the above object, the present invention provides the following technical solutions:

a production method of etherified oxygenated deep processing waste plastic oil comprises the following steps:

taking waste plastic oil obtained by pyrolyzing waste plastics as a raw material, adding 1-3 wt% of methanol and a small amount of catalyst into the waste plastic oil according to the weight percentage of the waste plastic oil under the conditions of 1 atmospheric pressure and 350-400 ℃, and carrying out homogeneous catalytic reaction to obtain oxygenated ether hydrocarbon fuel;

the catalyst comprises the following components in parts by weight:

wilkinson's catalyst RhCl (pph)₃)₃5 parts of composite alkali and 6 parts of composite alkali; wherein the composition of the composite alkali is as follows: 3 parts of potassium hydroxide and 3 parts of magnesium hydroxide.

As a preferable technical scheme of the invention, the adding amount of the catalyst is 0.1-0.3% of the total amount of the waste plastic oil.

In one embodiment of the present invention, the purity of the methanol is 99.0% or more.

As an implementable technical scheme of the invention, the reaction time of the homogeneous catalytic reaction is 10-20 s.

As an implementable technical scheme of the invention, the method for obtaining the waste plastic oil comprises the following steps: after heavy metals in the waste plastic are removed, condensing a vapor-liquid mixture (a mixed product obtained after pyrolysis of the waste plastic) at 250-300 ℃ and-0.4-0.8 MPa in an oxygen-free environment to obtain the waste plastic.

In the invention, the Wilkinson catalyst RhCl (pph) is creatively added into the catalyst₃)₃5 parts of composite alkali and 6 parts of composite alkali are used as catalyst combination, so that the effect of high-efficiency etherification under normal pressure is realized, crude oil (namely waste plastic oil) obtained by cracking waste plastics with very low combustion efficiency is subjected to etherification and oxygenation to obtain ether hydrocarbon fuel, and the emission (including NOx, CH and CO) of the ether hydrocarbon fuel is higher than that of national standard diesel oil (0)^#) And is a clean fuel.

In the course of the present invention studies, we have also found that the selection and proportion of the catalyst components of the present invention have a great influence on the emission of the ether hydrocarbon fuel obtained by the present invention, and even the ether hydrocarbon fuel cannot be obtained by the reaction at normal pressure (in the present invention, normal pressure refers to 1 atmosphere unless otherwise specified).

The invention has the following beneficial effects:

the invention can carry out etherification and oxygenation on the waste plastic oil under the normal pressure environment, thereby obtaining ether hydrocarbon fuel with low emission, solving the defects of harsh process conditions and difficult product having practical industrial application value in the prior art and having good market prospect.

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.

In the following examples, the catalyst is prepared from the Wilkinson's catalyst RhCl (pph) in parts by weight₃)₃5 parts of triphenylphosphine rhodium chloride (produced by Shanghai Tuo Si chemical Co., Ltd.) and 6 parts of composite alkali (3 parts of potassium hydroxide and 3 parts of magnesium hydroxide).

In the following examples, the waste plastic oil was obtained by the following method:

after heavy metals in the waste plastic are removed, condensing the vapor-liquid mixture at 250-300 ℃ and-0.4-0.8 MPa in an oxygen-free environment to obtain the composite material.

Example 1

Adding waste plastic oil into a normal-pressure reaction kettle, adding methanol according to 1% of the total weight of the waste plastic oil, fully stirring and mixing, then adding a catalyst according to 0.1% of the total weight of the waste plastic oil, fully stirring and mixing, and then carrying out homogeneous catalytic reaction under the conditions of 1 atmosphere pressure and 350 ℃, wherein the reaction time is 10s, so as to obtain the oxygenated ether hydrocarbon fuel.

Example 2

Adding waste plastic oil into an atmospheric pressure reaction kettle, then adding methanol according to 2% of the total weight of the waste plastic oil, fully stirring and mixing, then adding a catalyst according to 0.2% of the total weight of the waste plastic oil, fully stirring and mixing, and then carrying out homogeneous catalytic reaction under the conditions of 1 atmosphere pressure and 380 ℃ for 20s to obtain the oxygenated ether hydrocarbon fuel.

Example 3

Adding the waste plastic oil into an atmospheric pressure reaction kettle, then adding methanol according to 3% of the total weight of the waste plastic oil, fully stirring and mixing, then adding a catalyst according to 0.3% of the total weight of the waste plastic oil, fully stirring and mixing, and then carrying out homogeneous catalytic reaction under the conditions of 1 atmosphere pressure and 400 ℃, wherein the reaction time is 15s, so as to obtain the oxygenated ether hydrocarbon fuel.

Comparative example 1

With reference to example 1, the procedure was as in example 1 except that the catalyst lacked 3 parts of magnesium hydroxide as a component.

Comparative example 2

Reference is made to example 1, except that the catalyst deficiency is the component Wilkinson's catalyst RhCl (pph)₃)₃The balance, except 5, remained the same as in example 1.

Comparative example 3

Reference is made to example 1, except that the parts by weight of the components in the catalyst are Wilkinson's catalyst RhCl (pph)₃)₃The contents of the reaction mixture were kept in the same manner as in example 1 except for 2 parts by weight and 2 parts by weight of magnesium hydroxide.

Test example

Discharge amount experiment:

a DK4A diesel engine for scientific research is selected to carry out a bench test, the emission performance of the fuel obtained in the test at the working condition point corresponding to the load characteristic of 2400r/min of the engine is tested, and the fuel cannot react to generate ether hydrocarbon fuel according to the comparative example 2, so the experiment uses the example 1, the example 2, the example 3, the comparative example 1, the comparative example 3 and the national standard 0 to carry out the bench test^#The diesel fuel was used as a test subject, and the emission was examined in accordance with GB17930, and the results are shown in table 1.

TABLE 1