CN111410985A - Acid reduction method and system for coal-to-oil product - Google Patents
Acid reduction method and system for coal-to-oil product Download PDFInfo
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- CN111410985A CN111410985A CN202010196565.7A CN202010196565A CN111410985A CN 111410985 A CN111410985 A CN 111410985A CN 202010196565 A CN202010196565 A CN 202010196565A CN 111410985 A CN111410985 A CN 111410985A
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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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention aims to provide a method and a system for reducing acid of coal-to-liquid products. The method fully mixes the adsorbent and the coal-derived oil product in proportion at normal temperature and normal pressure and stands for a certain time, utilizes the strong adsorption capacity of the adsorbent to adsorb acidic substances in the coal-derived oil product into the adsorbent, and then separates the adsorbent from the coal-derived oil product after filtering to achieve the purpose of reducing the acidity of the coal-derived oil product, thereby solving the problems that the addition of strong acid and strong base caused by the prior method can corrode equipment, influence the health of human bodies, cause environmental pollution, difficult early transportation, high purchase cost and the like.
Description
Technical Field
The invention relates to a method and a system for reducing acid of coal-to-liquids.
Background
At present, the treatment of the acidity of petroleum products is mainly completed in the refining production link, and the oil products with over-standard acidity are produced, or the acidity indexes are strictly required to be further reduced although some acidity does not exceed the standard, for example, the acid reduction treatment of the finished oil of the space kerosene is a difficult problem in the field.
If the acidity in the space kerosene is raised to a certain extent, organic acid in the kerosene will have certain corrosivity to metals such as aluminum, magnesium and copper and non-metals such as rubber, and will also cause the kerosene to discolor and thermochemical stability to be poor, thus influencing the storage, transportation and use of the kerosene.
At present, the alkali washing method is the most widely adopted acid reduction treatment means in oil refineries, but has great limitation on raw materials due to the following reasons: the introduction of strong acid and strong base is needed in the alkali washing process, which brings the following two problems:
1. the strong acid solution and the strong base solution have high concentration, so that the strong acid solution can corrode human bodies and equipment, and particularly, the strong acid solution can volatilize strong acid gas when in use, so that the health of people can be influenced, the difficulty of sewage treatment is increased, and the environment is polluted.
2. The strong acid solution and the strong alkali solution both belong to dangerous transport products, and can be transported to the site by special protective vehicles and stored in an acid-base storage tank only after being approved by relevant departments during purchase. Therefore, strong acid and strong base are purchased, the procedure is complex, the transportation cost is high, and the transportation risk is high.
Disclosure of Invention
The invention aims to provide a method and a system for reducing the acidity of coal-to-liquid products, and the method is applied to the treatment of the acidity of space kerosene, so that the technical problem in the field is solved, and the problems that equipment is corroded, the human health is influenced, the environment is polluted, the early-stage transportation is difficult, the purchase cost is high and the like due to the addition of strong acid and strong alkali caused by the existing method are solved.
The basic principle of the invention is as follows:
fully mixing the adsorbent and the coal-derived oil product in proportion at normal temperature and normal pressure, standing for a certain time, adsorbing acidic substances in the coal-derived oil product into the adsorbent by utilizing the strong adsorption capacity of the adsorbent, and filtering to separate the adsorbent from the coal-derived oil product so as to achieve the purpose of reducing the acidity of the coal-derived oil product.
The specific technical scheme of the invention is as follows:
the invention provides a deacidification method for coal-to-oil products, which comprises the following steps:
mixing an adsorbent and the coal oil product to be deacidified in a mass ratio of 1:100-1:30, standing for 1-10 days, and separating the coal oil product from the adsorbent to obtain the coal oil product with qualified acidity; the adsorbent is ion exchange resin, alkaline silica gel, active Al2O3Any one or more combinations thereof.
Further, the oil products prepared from coal to be deacidified are direct liquefied coal oil, indirect liquefied coal oil and coal tar hydrogenated oil.
Furthermore, after the coal-derived oil product and the adsorbent are mixed, the adsorption effect can be enhanced by a mechanical stirring or pump circulation mode.
Further, the oil product prepared from the coal to be deacidified is separated from the adsorbent by a standing separation method or by filtering through a filter.
The invention also provides a deacidification system for the coal-to-liquid oil product, which comprises a storage container for the coal-to-liquid oil product to be deacidified, a mixing container and a storage container for the deacidified coal-to-liquid oil product; the storage containers of the coal-to-be-deacidified oil products are communicated with the mixing containers through first pipelines, and the storage containers of the deacidified coal-to-be-deacidified oil products are communicated with each other through second pipelines; install first oil pump and second oil pump on first pipeline and the second pipeline respectively, be equipped with the filter on the pipeline between deacidified coal system oil storage container and the second oil pump, all install the stop valve on first pipeline, the second pipeline.
Furthermore, a bypass pipeline is further arranged between the mixing container and the second oil pump, and a stop valve is installed on the bypass pipeline.
Further, a stirring device is arranged in the mixing container.
The invention has the beneficial effects that:
1. the method disclosed by the invention can reduce the acidity of the kerosene product by at least 90% by only utilizing the adsorption capacity of the adsorbent, avoids the influence on equipment corrosion, human health and environment compared with the existing alkali washing method without adding strong acid and strong base, solves the problems of complex procedures for transporting the strong acid and the strong base, high transportation cost and large transportation risk in the alkali washing method, and is simple in implementation mode.
2. The invention adopts three containers and two oil pumps to form the acid reduction system, has simple structure and is beneficial to industrial popularization and application.
Drawings
FIG. 1 is a schematic diagram of the acid reduction system;
figure 2 is a graph of acid reduction efficiency.
The reference numbers are as follows:
1-a storage container for coal-to-be-deacidified oil product, 2-a mixing container, 3-a storage container for deacidified coal-to-oil product, 4-a first pipeline, 5-a second pipeline, 6-a first oil pump, 7-a second oil pump, 8-a filter, 9-a bypass pipeline and 10-a stop valve.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a deacidification method for coal-to-oil products, which is basically realized by mixing an adsorbent and an acid to be deacidifiedMixing the coal-derived oil product in a mass ratio of 1:100-1:30 (after the coal-derived oil product and the adsorbent are mixed, the adsorption effect can be enhanced by a mechanical stirring or pump circulation mode), standing for 1-10 days, and then separating the coal-derived oil product from the adsorbent (the coal-derived oil product and the adsorbent are separated by a standing separation method or filtration through a filter), so as to obtain the coal-derived oil product with qualified acidity; the adsorbent is ion exchange resin or alkaline silica gel or active Al2O3Any one or more combinations thereof. Wherein, the oil product of coal to be deacidified can be direct liquefied coal oil, indirect liquefied coal oil, coal tar hydrogenated oil.
Based on the method, the invention provides an acid reduction system for coal-to-liquids, the specific structure of which is shown in fig. 1, and the acid reduction system comprises a coal-to-liquids storage container 1 to be deacidified, a mixing container 2 and a deacidified coal-to-liquids storage container 3; the storage containers 1 and the mixing containers 2 of the coal-to-oil products to be deacidified are communicated through first pipelines 4, and the storage containers 3 of the coal-to-oil products after deacidification are communicated through second pipelines 5; install first oil pump 6 and second oil pump 7 on first pipeline 4 and the second pipeline 5 respectively, be equipped with filter 8 on the pipeline between deacidification coal system oil storage container 3 and the second oil pump 7, all install stop valve 10 on first pipeline, the second pipeline.
In order to make the mixing effect better, the invention also provides two auxiliary mixing means:
the first method comprises the following steps: still be equipped with by pass line 9 between mixing container 2 and second oil pump 7, install stop valve 10 on the by pass line 9, open second oil pump 7 and stop valve and make the mixed liquid in mixing container 2 circulate, make adsorbent and the coal-to-be-deacidified system oil intensive mixing.
And the second method comprises the following steps: be equipped with agitating unit in mixing vessel, make adsorbent and the coal-to-liquids intensive mixing that treats deacidification through the mode of stirring.
Example one
1. Conveying 300kg of space kerosene in a coal oil product storage container to be deacidified into a mixing container by using a first oil pump, and simultaneously adding 3kg of FNG-II alkaline silica gel into the mixing container;
2. and during the standing period of 240 hours, pumping out the oil in the mixing container by using a second oil pump every 24 hours, and feeding the oil back into the mixing container through a bypass pipeline for circulation once, so that the space kerosene and the FNG-II basic silica gel are fully and uniformly mixed.
3. After the space kerosene and the FNG-II alkaline silica gel are uniformly mixed, sampling and testing the acidity of the oil product, and reducing the acidity of the sampled and tested oil product from 23.22 to 0.39.
Example two
1. Conveying 300kg of coal-based space kerosene in a coal oil product storage container to be deacidified into a mixing container by using a first oil pump, and simultaneously adding 5kg of FNG-II alkaline silica gel into the mixing container;
2. and during standing for 168 hours, pumping out the oil in the mixing container by using a second oil pump every 24 hours, and feeding the oil back to the mixing container through a bypass pipeline for circulation once, so that the space kerosene and the FNG-II basic silica gel are fully and uniformly mixed.
3. After the space kerosene and the FNG-II alkaline silica gel are uniformly mixed, sampling and testing the acidity of the oil, and reducing the acidity of the sampled and tested oil from 23.32 to 0.32.
EXAMPLE III
1. 300kg of coal-based space kerosene in a coal oil product storage container to be deacidified is conveyed into a mixing container by a first oil pump, and 10kg of FNG-II alkaline silica gel is added into the mixing container;
2. and during standing for 60 hours, pumping out the oil in the mixing container by using a second oil pump every 24 hours, and feeding the oil back into the mixing container through a bypass pipeline for circulation once, so that the space kerosene and the FNG-II basic silica gel are fully and uniformly mixed.
3. After the space kerosene and the FNG-II alkaline silica gel are uniformly mixed, sampling and testing the acidity of the oil, and reducing the acidity of the sampled and tested oil from 23.32 to 0.24.
The mixing proportion of the adsorbent and the coal-to-oil product to be deacidified and the standing time have obvious influence on the deacidification effect and the deacidification efficiency, the initial acidity value of the oil product is also considered in practical application, a sample is regularly sampled in the standing process to test and monitor the change condition of the acidity of the oil product, and the mixing proportion and the standing time are adjusted in time according to the monitoring result to ensure that the deacidification effect and the deacidification efficiency are optimal.
Because the mixing ratio of the adsorbent and the coal-to-oil product to be deacidified and the standing time have obvious influence on the deacidification effect and the deacidification efficiency, the influence of the addition amount of the adsorbent and the standing time on the deacidification effect of the high-acidity formula oil is analyzed through experiments.
Firstly, 10g, 30g and 50g of alkaline silica gel are respectively and uniformly mixed with 1000m L space kerosene as an adsorbent, standing for 24h and then detecting the acidity of the space kerosene, then, 30g of silica gel is selected and uniformly mixed with 1000m L space kerosene, and the change rule of the acidity of the space kerosene is examined when the space kerosene is standing for 48h, 96h and 240 h.
When the silica gel was added at 50g for 240h, the acidity decreased from 23.22mgKOH/100m L to 0.30mgKOH/100m L.
Change in acidity
As shown in FIG. 2, the acid reduction process by the adsorption method provided by the invention has the advantages that the acid reduction rate is very high in the early stage and tends to be gentle in a certain stage. The silica gel reaches adsorption saturation in 48 hours, and 94.18% of acidic substances are removed; 98.71 percent of acidic substances are removed in 240 hours. Therefore, the reasonable standing time of the silica gel adsorption deacidification process is determined according to the actual condition of the initial acidity of the formula oil, and the acidity change rule can be continuously sampled and monitored in the standing process.
Claims (7)
1. The acid reduction method for the coal-to-oil product is characterized by comprising the following steps:
mixing an adsorbent and the coal oil product to be deacidified in a mass ratio of 1:100-1:30, standing for 1-10 days, and separating the coal oil product from the adsorbent to obtain the coal oil product with qualified acidity; the adsorbent is ion exchange resin, alkaline silica gel, active Al2O3Any one or more combinations thereof.
2. The method for reducing the acidity of coal-to-liquids according to claim 1, characterized in that: the coal-to-oil product to be deacidified is direct liquefied coal-to-oil, indirect liquefied coal-to-oil and coal tar hydrogenated oil.
3. The method for reducing the acidity of coal-to-liquids according to claim 1, wherein: after the coal-derived oil product and the adsorbent are mixed, the adsorption effect can be enhanced by a mechanical stirring or pump circulation mode.
4. The method for reducing the acidity of coal-to-liquids according to claim 1, wherein: and (3) separating the oil product of the coal to be deacidified from the adsorbent by adopting a standing separation method or filtering through a filter.
5. The utility model provides a deacidification system of coal system oil which characterized in that: comprises a storage container for the coal-to-be-deacidified oil product, a mixing container and a storage container for the deacidified coal-to-oil product; the storage containers of the coal-to-be-deacidified oil products are communicated with the mixing containers through first pipelines, and the storage containers of the deacidified coal-to-be-deacidified oil products are communicated with each other through second pipelines; install first oil pump and second oil pump on first pipeline and the second pipeline respectively, be equipped with the filter on the pipeline between deacidified coal system oil storage container and the second oil pump, all install the stop valve on first pipeline, the second pipeline.
6. The coal-to-liquids deacidification system according to claim 5, wherein: still be equipped with the by-pass pipeline between mixing vessel and the second oil pump, install the stop valve on the by-pass pipeline.
7. The coal-to-liquids deacidification system according to claim 5, wherein: and a stirring device is arranged in the mixing container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010196565.7A CN111410985A (en) | 2020-03-19 | 2020-03-19 | Acid reduction method and system for coal-to-oil product |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010196565.7A CN111410985A (en) | 2020-03-19 | 2020-03-19 | Acid reduction method and system for coal-to-oil product |
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| CN111410985A true CN111410985A (en) | 2020-07-14 |
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Citations (4)
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| CN101955792A (en) * | 2010-08-30 | 2011-01-26 | 广西大学 | Method for adsorption deacidification of diesel oil and production of bentonite naphthenate |
| CN106986765A (en) * | 2017-04-26 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of high temperature modification pentaerythritol ester and preparation method thereof |
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2020
- 2020-03-19 CN CN202010196565.7A patent/CN111410985A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955792A (en) * | 2010-08-30 | 2011-01-26 | 广西大学 | Method for adsorption deacidification of diesel oil and production of bentonite naphthenate |
| CN106986765A (en) * | 2017-04-26 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of high temperature modification pentaerythritol ester and preparation method thereof |
| CN107282004A (en) * | 2017-07-17 | 2017-10-24 | ***后勤保障部油料研究所 | It is a kind of for solid base deacidification agent of polymethoxy dialkyl ether depickling subtractive process and preparation method thereof |
| CN109418680A (en) * | 2017-08-22 | 2019-03-05 | 秭归县屈姑食品有限公司 | A kind of de- hardship tank of depickling for during fruit juice production |
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