CN109201025B - Regeneration method of petroleum waste carclazyte - Google Patents

Regeneration method of petroleum waste carclazyte Download PDF

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CN109201025B
CN109201025B CN201811425201.0A CN201811425201A CN109201025B CN 109201025 B CN109201025 B CN 109201025B CN 201811425201 A CN201811425201 A CN 201811425201A CN 109201025 B CN109201025 B CN 109201025B
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argil
clay
petroleum
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CN109201025A (en
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袁勇
雷冲天
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Yuan Yong
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Foshan Guangye Environmental Protection Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/345Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3433Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425

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Abstract

The invention provides a method for regenerating petroleum spent bleaching clay, which specifically comprises the following steps: step (1): mixing an ester organic solvent and an ether organic solvent to obtain a double-solvent extracting agent; step (2): extracting the petroleum waste carclazyte adsorbate by using the extracting agent prepared in the step (1); and (3): separating the extracted petroleum spent bleaching clay from the extracting agent to obtain wet bleaching clay and mixed oil; and (4): the wet clay is dried in vacuum and activated in a rotary way to obtain the activated clay which can be reused. The method has the advantages that the ester and the ether are mixed according to a certain proportion to be used as an extracting agent, the petroleum spent bleaching earth is extracted and then regenerated, the extraction effect is good, the adsorption capacity of the obtained regenerated bleaching earth is strong, the regenerated bleaching earth meets the requirement standard of the industry on the bleaching earth for oil refining, and the regenerated bleaching earth can be reused; the recovered white clay oil can also be used as an asphalt auxiliary material without treatment or discharge; the preferred sec-butyl acetate and methyl tert-butyl ether are bulk feeds and are readily available.

Description

Regeneration method of petroleum waste carclazyte
Technical Field
The invention relates to a method for regenerating waste argil, in particular to a method for regenerating petroleum waste argil.
Background
In the process of petroleum refining, activated clay is usually adopted for adsorption decoloration and impurity removal, the activated white body adsorbs a certain amount of impurities and also adsorbs more petroleum products, and the white clay becomes oily petroleum waste white clay after being adsorbed to saturation along with the increase of the adsorption amount, so that the white clay becomes brown solid waste. Not only influences the normal production work of the oil refinery, but also causes great pollution to the ecological environment.
The traditional treatment method is a landfill or incineration method, but after the waste argil is buried, organic impurities, namely other harmful substances, in the waste argil still cause serious pollution to farmlands, rivers, underground water and the like, the waste argil only removes organic matters in the waste argil after incineration, and the waste argil after incineration still needs to be buried. Some enterprises also use hot alkaline water to wash and separate substances adsorbed by the waste argil, but a large amount of water and energy are consumed, the generated fluid argil is in an emulsified state, subsequent treatment is difficult, the cyclic utilization rate of process water is not high, secondly, a large amount of greenhouse gases and toxic argil tail water are discharged to generate long-term harmful influence on the environment, and the hot alkaline water washing is not applicable to the separation of all the waste argil.
In the present year, the method of organic solvent extraction is used for regenerating petroleum waste carclazyte, the used organic solvent mainly comprises No. 6 solvent oil, n-hexane, petroleum ether, methanol and the like, the extraction is not clean, and the recovery rate of the carclazyte oil is low.
Disclosure of Invention
The invention aims to provide a regeneration method of petroleum waste carclazyte, which utilizes ester-ether combination as an extracting agent to extract and regenerate the waste carclazyte, has good extraction effect and high carclazyte oil recovery rate, and the obtained regenerated carclazyte has strong adsorption capacity.
The technical scheme of the invention is as follows:
a regeneration method of petroleum spent bleaching clay specifically comprises the following steps:
step (1): mixing an ester organic solvent and an ether organic solvent to obtain a double-solvent extracting agent;
step (2): extracting the petroleum waste carclazyte adsorbate by using the extracting agent prepared in the step (1);
and (3): separating the extracted petroleum spent bleaching clay from the extracting agent to obtain wet bleaching clay and mixed oil;
and (4): the wet clay is dried in vacuum and activated in a rotary way to obtain the activated clay which can be reused.
The regeneration method for the petroleum spent bleaching clay comprises the step (1), wherein the ester organic solvent is sec-butyl acetate, and the ether organic solvent is methyl tert-butyl ether.
The regeneration method for the petroleum spent bleaching clay comprises the step (1), wherein the volume ratio of the sec-butyl acetate to the methyl tert-butyl ether is 1:4-4: 1.
The regeneration method for the petroleum spent bleaching earth is characterized in that in the step (2), the petroleum spent bleaching earth is used as lubricating oil, and the volume ratio of the sec-butyl acetate to the methyl tert-butyl ether in the step (1) is 1:1-4: 1.
The regeneration method for the petroleum spent bleaching earth is characterized in that in the step (2), the petroleum spent bleaching earth is used for diesel oil, and the volume ratio of the sec-butyl acetate to the methyl tert-butyl ether in the step (1) is 1:1-1: 4.
The regeneration method for the petroleum spent bleaching clay is characterized in that in the step (2), the extraction temperature is 30-60 ℃.
The regeneration method for the petroleum spent bleaching clay is characterized in that in the step (2), the dosage of the extracting agent is 1-4 times of that of the spent bleaching clay.
The regeneration method for the petroleum spent bleaching clay comprises the step (3), wherein in the step (3), the mixed oil is subjected to reduced pressure distillation and recovered to obtain an extracting agent and bleaching clay oil.
The regeneration method for the petroleum waste carclazyte is characterized in that in the step (3), the mixed oil is subjected to the following steps of recovering an extracting agent and carclazyte oil: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. and after the sec-butyl acetate is steamed, stopping heating, and obtaining cooled residual liquid, namely the argil oil.
The invention has the beneficial effects that:
the method has the advantages that the ester and the ether are mixed according to a certain proportion to be used as an extracting agent, the petroleum spent bleaching earth is extracted and then regenerated, the extraction effect is good, the adsorption capacity of the obtained regenerated bleaching earth is strong, the regenerated bleaching earth meets the requirement standard of the industry on the bleaching earth for oil refining, and the regenerated bleaching earth can be reused; the recovered white clay oil can also be used as an asphalt auxiliary material without treatment or discharge; the preferred sec-butyl acetate and methyl tert-butyl ether are bulk raw materials and are easy to obtain; the boiling points of the esters and ethers used are very different from the boiling point of white clay oil, and the solvent is easily recovered by distillation after extraction.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
Example 1
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 4; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 30 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 153g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. And weighing to obtain 46.3g of white clay oil which can be used as an asphalt auxiliary material, wherein the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing the mixed extracting agent again. In this example, 5 sets of experiments were arranged in parallel, and the above results were the average of the results of 3 sets of experiments (the same applies below).
Example 2
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 4; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 30 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 157g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 41.7g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 3
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 3; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 40 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 147g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 51.42g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 4
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 3; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 40 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 157g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 41.78g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 5
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 2; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 50 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 148g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 52.3g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extracting agent again.
Example 6
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 2; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 50 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 157g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 41.8g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 7
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 1; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 60 ℃; filtering to obtain wet waste clay and mixed oil; and (3) drying the wet argil in vacuum, and performing rotary activation to obtain 150g of regenerated activated argil, wherein the mixed oil is prepared by recovering an extracting agent and argil oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 48.54g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 8
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 1: 1; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 60 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 148g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 51.3g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 9
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 2: 1; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 60 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 158g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 40.5g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extracting agent again.
Example 10
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 2: 1; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 60 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 145g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 53.52g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 11
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 3: 1; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 50 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 159g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 39.84g after weighing, and can be used as an asphalt auxiliary material, and the methyl tert-butyl ether and sec-butyl acetate obtained by extraction and recovery can be used for preparing a mixed extraction agent again.
Example 12
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained after sec-butyl acetate and methyl tert-butyl ether are uniformly mixed in a ratio of 3: 1; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 50 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 147g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 51.72g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Example 13
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained by uniformly mixing sec-butyl acetate and methyl tert-butyl ether at a ratio of 4: 1; weighing 200g of waste argil used in the process of refining diesel oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 40 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 159g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 40.12g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extracting agent again.
Example 14
The process flow diagram of this example is shown in fig. 1, and a double-solvent extraction agent is obtained by uniformly mixing sec-butyl acetate and methyl tert-butyl ether at a ratio of 4: 1; weighing 200g of waste argil used in the process of refining lubricating oil by a certain oil refinery, adding 500ml of prepared extracting agent, and stirring for 20 minutes at 40 ℃; filtering to obtain wet waste clay and mixed oil; and (3) carrying out vacuum drying and rotary activation on the wet argil to obtain 151g of regenerated activated argil, and recovering the extractant and the argil oil from the mixed oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. after the sec-butyl acetate is steamed, the heating is stopped, and the cooled residual liquid is brown oil, the main component of which is the adsorbate of argil in the process of refining petroleum, which is called argil oil. The obtained white clay oil is 47.46g after weighing, and can be used as an asphalt auxiliary material, and the recovered methyl tert-butyl ether and sec-butyl acetate can be used for preparing a mixed extraction agent again.
Performance detection and data analysis of the regenerated activated clay:
the regenerated activated clay obtained in each example was collected, and the performance of the regenerated activated clay was examined with reference to HG/T2569-94, and the recovery rate of the clay oil in each example was counted, and the results are shown in table 1.
TABLE 1 comparison of examples
Group of Kind of waste clay Esters/ethers (V/V) Clay oil recovery (%) Activity of regenerated activated clay Decolorization rate of regenerated activated clay Free acid of regenerated activated clay
Example 1 Waste argil for diesel oil 1:4 23.15 224 88% 0.13%
Example 2 Spent bleaching clay for lubricating oil 1:4 20.85 209 83% 0.16%
Example 3 Waste argil for diesel oil 1:3 25.71 226 91% 0.11%
Example 4 Spent bleaching clay for lubricating oil 1:3 20.89 217 85% 0.16%
Example 5 Waste argil for diesel oil 1:2 26.8 234 94% 0.10%
Example 6 Spent bleaching clay for lubricating oil 1:2 20.9 212 90% 0.17%
Example 7 Waste argil for diesel oil 1:1 24.27 228 91% 0.10%
Example 8 Spent bleaching clay for lubricating oil 1:1 25.65 228 93% 0.10%
Example 9 Waste argil for diesel oil 2:1 20.25 203 89% 0.18%
Example 10 Spent bleaching clay for lubricating oil 2:1 26.76 235 93% 0.10%
Example 11 Waste argil for diesel oil 3:1 19.92 208 86% 0.20%
Example 12 Spent bleaching clay for lubricating oil 3:1 25.86 230 90% 0.11%
Example 13 Waste argil for diesel oil 4:1 20.06 211 85% 0.15%
Example 14 Spent bleaching clay for lubricating oil 4:1 23.73 224 88% 0.13%
As can be seen from the above table, different ester ether ratios are used to extract different types of waste clay for petroleum, and the obtained clay oil has different recovery rates, i.e., the complete degree of extraction of the adsorbate of the waste clay is different. The ether polyester is less beneficial to the extraction regeneration of the spent bleaching clay for diesel oil, and the ether polyester is more beneficial to the extraction regeneration of the spent bleaching clay for lubricating oil. Wherein when the waste argil is used for diesel oil, the effect of the extractant prepared by mixing sec-butyl acetate and methyl tert-butyl ether in a ratio of 1:2 is optimal; when the waste clay is used as the waste clay for lubricating oil, the effect of the extractant prepared by mixing the sec-butyl acetate and the methyl tert-butyl ether in a ratio of 2:1 is optimal. This may be because: the waste clay for diesel oil absorbs a large amount of substances such as colloid, alkane, polycyclic aromatic hydrocarbon, polyether and the like, and also a small amount of asphaltene, polyesters, sulfonate and the like, and the methyl tert-butyl ether has very good solubility to the asphaltene, the alkane, the polycyclic aromatic hydrocarbon and the polyether, so that the best effect is achieved when the ratio of the sec-butyl acetate to the methyl tert-butyl ether is 1: 2; the waste argil for the lubricating oil adsorbs a large amount of asphaltene, polyester, sulfonate, a small amount of colloid, alkane, polyether and the like, and the sec-butyl acetate has good solubility on the asphaltene, the polyester, the sulfonate and other components, so that the effect is optimal when the ratio of the sec-butyl acetate to the methyl tert-butyl ether is 2: 1.
In addition, the examples with high clay oil recovery rate show better performance in the aspects of activity, decolorization rate, fatty acid content and the like of the obtained regenerated clay, and further show that the examples have better effect of extracting and removing impurities from the petroleum waste clay.
Comparative example:
in order to further verify the technical effect of the invention, the following steps of preparing the extracting agent by respectively compounding common organic solvents in the prior art, and performing operations such as extraction, filtration, drying, distillation, rotary regeneration and the like by the same method are taken as comparative examples. Wherein, the components and the mixture ratio of the solvent of the comparative example are shown in table 2, and the recovery rate of the obtained clay oil and the performance of the regenerated activated clay are shown in table 3.
TABLE 2 Components and proportions of solvents in the respective proportions
Group of Kind of waste clay Solvent A Solvent B Solvent A/solvent B (v/v)
Comparative example 1 Waste argil for diesel oil Methanol Petroleum ether 2:1
Comparative example 2 Spent bleaching clay for lubricating oil Methanol Petroleum ether 2:1
Comparative example 3 Waste argil for diesel oil Ethanol No. 6 solvent oil 1:2
Comparative example 4 Spent bleaching clay for lubricating oil Ethanol No. 6 solvent oil 1:2
Comparative example 5 Waste argil for diesel oil N-hexane Petroleum ether 1:1
Comparative example 6 Spent bleaching clay for lubricating oil N-hexane Petroleum ether 1:1
TABLE 3 Clay oil recovery and Performance of the resulting regenerated activated Clay for each scale
Group of Clay oil recovery (%) Activity of regenerated activated clay Decolorization rate of regenerated activated clay Free acid of regenerated activated clay
Comparative example 1 17.23 189 72% 0.41
Comparative example 2 12.2 154 60% 0.68
Comparative example 3 13.82 159 60% 0.60
Comparative example 4 17.57 190 74% 0.42
Comparative example 5 15.36 167 67% 0.52
Comparative example 6 16.84 173 69% 0.43
As can be seen from tables 2 and 3, compared with the prior art, the extraction effect is good and the adsorption capacity of the obtained regenerated clay is strong by using the mixture of the sec-butyl acetate and the methyl tert-butyl ether according to a proper proportion as the extracting agent; and the used raw materials of sec-butyl acetate and methyl tert-butyl ether are bulk raw materials and are easy to obtain. And the extractant can be easily separated from the argil oil by distillation.
It is understood that, as for the amount of the extractant, it is theoretically better as it is larger, but the present invention limits the amount of the extractant to 1 to 4 times the amount of the clay in consideration of energy consumption in recovering the solvent. The clay after extraction and drying in the invention can be activated by the conventional activation method in the prior art. In the extraction process, the stirring or shaking can be carried out by a method commonly used in a laboratory, and the prior industrialized extraction machine or extractor can also be adopted. Having thus described the invention in detail, it will be apparent to those skilled in the art that modifications and variations are possible in light of the above teachings, and it is intended to cover all such modifications and variations as fall within the true scope of the invention as defined by the appended claims.

Claims (4)

1. A regeneration method for petroleum spent bleaching clay is characterized by comprising the following steps:
step (1): mixing an ester organic solvent and an ether organic solvent to obtain a double-solvent extracting agent;
step (2): extracting the petroleum waste carclazyte adsorbate by using the extracting agent prepared in the step (1);
and (3): separating the extracted petroleum spent bleaching clay from the extracting agent to obtain wet bleaching clay and mixed oil; distilling and recovering the mixed oil to obtain an extracting agent and argil oil;
and (4): the wet argil is subjected to vacuum drying and rotary activation to obtain activated argil which can be recycled;
in the step (1), the ester organic solvent is sec-butyl acetate, and the ether organic solvent is methyl tert-butyl ether;
in the step (2), when the petroleum waste argil is used as lubricating oil waste argil, the volume ratio of the sec-butyl acetate to the methyl tert-butyl ether in the step (1) is 1:1-4: 1;
in the step (2), when the petroleum waste argil is used for diesel oil, the volume ratio of the sec-butyl acetate to the methyl tert-butyl ether in the step (1) is 1:1-1: 4.
2. The process of claim 1, wherein the extraction temperature in step (2) is 30-60 ℃.
3. The process of claim 1, wherein in step (2), the amount of the extractant used is 1-4 times the amount of the spent bleaching earth.
4. The regeneration method of petroleum-based spent bleaching clay according to claim 1, wherein in the step (3), the mixed oil is used for recovering the extractant and the bleaching clay oil through the following steps: A. distilling the mixed solution at 60-80 deg.C, and collecting the first fraction to obtain methyl tert-butyl ether; B. after the methyl tert-butyl ether is evaporated, increasing the temperature of the mixed solution, continuously distilling the mixed solution within the temperature range of 110-120 ℃, and collecting a second fraction to obtain sec-butyl acetate; C. and after the sec-butyl acetate is steamed, stopping heating, and obtaining cooled residual liquid, namely the argil oil.
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