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Catalyst for esterification deacidification of crude oil and distillate oil and process thereof

A technology of esterification, deacidification, and catalyst, which is applied in the petroleum industry, refining hydrocarbon oil, etc., and can solve problems such as hydrogen consumption, environmental pollution, and high equipment investment

Inactive Publication Date: 2005-09-21
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are many methods for removing naphthenic acid at present, such as hydrofinishing, alkali washing, alcohol-ammonia and esterification. The aforementioned three methods have their scope of use and limitations: Consumption of hydrogen, high equipment investment, and high operating costs; alkali washing method consumes a large amount of alkali, pollutes the environment, and is easy to form emulsification; ethanol-ammonia method and isopropanol-ammonia method solvent recovery costs are too high, which is unbearable in the industry
In the absence of a catalyst, esterification and deacidification require a very high temperature (such as more than 300 ° C) to be relatively complete, and require a large excess of alcohols, so it is economically unbearable

Method used

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  • Catalyst for esterification deacidification of crude oil and distillate oil and process thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0010] In a laboratory fixed-bed reactor, the above-mentioned catalyst is loaded, and the composition of the catalyst is: the carrier is alumina, the active component is Sn, and the content of Sn is 20 (w)%. The inner diameter of the reactor is 26mm and the length is 500mm , the height of catalyzer is 450mm, feeds with metering pump, raw material oil is certain crude oil, and its acid value is 3.9mgKOH / g, and methyl alcohol is esterification deacidification agent, and methyl alcohol accounts for raw material oil 1% (weight), earlier methyl alcohol and The crude oil is mixed well, and then fed with a pump, the reaction temperature of the reactor bed is 250°C, the reaction pressure is 0.2MPa, and the space velocity is 2hr -1 , after stable operation for 4hr, the acid value of deacidified oleic acid was recorded as 0.3mgKOH / g, and the deacidified oil was 92.3%. Unreacted methanol was contained in the deacidified oil, and methanol accounted for 0.6% (weight) of raw oil by distillat...

Embodiment 2

[0013] Using the same reactor as Example 1, the stock oil is a second-line distillate under reduced pressure, with a distillation range of 350-420° C. and an acid value of 3.8 mgKOH / g. Using methanol as an esterification deacidification agent, the consumption accounts for 0.5% of the crude oil. The composition of the catalyst is as follows: the carrier is molecular sieve, the active components are Sn and Zn, accounting for 4.6% (weight) of the catalyst, wherein Sn accounts for 3.1% of the catalyst, and Zn accounts for 1.5% of the catalyst. The bed temperature of the reactor is 270°C, the space velocity is 1, and the reaction pressure is 0.5 MPa. After stable operation, the acid value of the deacidified oil is 0.36 mgKOH / g, and the deacidification rate is 90.5%. Using other carriers such as diatomaceous earth, clay, and silica gel to support Sn and Zn also has good results.

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Abstract

The invention discloses a process for lowering acid value of crude oil and distillate oil, which comprises proceeding esterification reaction by menthol with crude oil or naphthenic acid in distillate oil, producing naphthenic acid ester in fixed bed reactor equipped with catalyst, then recovering the non-reacted methanol through distillation. The catalyst comprises carrying agent, which includes aluminium oxide, silica gel, molecular sieve, diatomite and carclazyte, amounting to 20-98 wt% of the catalyst, and active component including Sn or Zn, amounting to 2-40 wt% of the catalyst.

Description

technical field [0001] The invention belongs to the field of refining petroleum and its petroleum fractions, and relates to the removal of acidic substances in petroleum or petroleum fractions. The International Patent Classification belongs to C10G 19 / 00. Background technique [0002] Petroleum and its fractions contain some acidic substances, referred to as petroleum acids. The main component of these acidic substances is naphthenic acid. The existence of naphthenic acid not only corrodes equipment, but also affects the color and stability of petroleum products. Therefore, during petroleum refining The naphthenic acid should be removed. There are many methods for removing naphthenic acid at present, such as hydrofinishing, alkali washing, alcohol-ammonia and esterification. The aforementioned three methods have their scope of use and limitations: Hydrogen is consumed, equipment investment is high, and operating costs are also high; the alkali washing method consumes a la...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G29/22
Inventor 王延臻刘艳苹刘晨光张苗苗袁洪娟
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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