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Sorbent for reducing sulfide in light hydrocarbon oil

A technology of adsorbent and sulfide, applied in the direction of refined hydrocarbon oil, petroleum industry, etc., can solve the problems of insufficient depth desulfurization and loss of octane number of gasoline products, etc., achieve uniform distribution of adsorbents, increase gasoline octane number, Good desulfurization effect

Active Publication Date: 2009-05-20
CHINA PETROLEUM & CHEM CORP +1
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Problems solved by technology

Although the above-mentioned patents have achieved deep desulfurization of hydrocarbon oils under low hydrogen consumption, the octane number of gasoline products still has a slight loss
[0004] CN1261218C, CN1583973A, and CN1583972A all use zeolite desulfurizers to crack and desulfurize light oil products under non-hydrogen-facing conditions, and selectively crack sulfides to convert them into hydrocarbons and inorganic sulfides without hydrogen consumption and octane loss, but , like heavy oil catalytic cracking desulfurization, its desulfurization rate is affected by the sulfur content of raw materials, catalyst properties and conversion depth, etc., which is not enough to achieve deep desulfurization. The desulfurization rate is generally 50-80%, and it can only be used to produce low-sulfur refined oil. , low octane loss

Method used

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  • Sorbent for reducing sulfide in light hydrocarbon oil

Examples

Experimental program
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Effect test

preparation example Construction

[0049] The preparation of the adsorbent solid particles used in this embodiment is as follows:

[0050] The main raw materials of the carrier used in this embodiment are as follows:

[0051] 1 # Carrier: 10 kg of pseudo-boehmite (solid content is 64% by weight, industrial product of Shandong Zibo Aluminum Factory, the same below) + 1.0 kg of silica sol (solid content is 25% by weight, produced by Qingdao Lifan Chemical Factory, the same below) +13.1 kilograms of zinc oxide (purity 99.7%, product of Cangzhou Jiewei Chemical Co., Ltd.);

[0052] 2 # Carrier: 4 kilograms of pseudoboehmite+1.0 kilogram of silica sol+6 kilograms of kaolin (solid content is 73% by weight, produced by Suzhou China Clay Company)+10 kilograms of zinc hydroxide (zinc oxide content 71.5%, Peixian Zinc Oxide Factory product);

[0053] 3 # Carrier: 5 kg of pseudo-boehmite+4 kg of kaolin+2 kg of cumulated clay (solid content is 68% by weight, produced by Hubei Zhongxiang)+3.5 kg of zinc sulfate (purity...

Embodiment 1-3

[0063] Examples 1-3 illustrate the adsorbent composition and preparation method of phosphorus-containing modified rare earth shape-selective zeolite.

[0064]7.5 kg of nickel chloride produced by Zhangjiagang Huayi Chemical Co., Ltd., and 8.5 kg of metal salt mixtures of cobalt nitrate and nickel nitrate were formulated into aqueous solutions with a metal ion concentration of 1 to 10 mol / L for use.

[0065] Mix nickel chloride aqueous solution with P-RE-ZSM5 / 1 at room temperature # Mix the carrier, add ammonia water with a concentration of 3mol / L while stirring, maintain the pH at 7-10, keep stirring until the precipitation is complete, raise the temperature to 90°C and leave it to age for at least 0.5 hours, filter, and wash the filter cake until it is free of acid ions The mixture of nickel hydroxide, P-RE-ZSM5 and alumina carrier material is obtained, and washed with water until there is no chloride ion. After drying at 100-200°C for at least 2 hours, then roasting at 500-...

Embodiment 4-5

[0074] Examples 4-5 illustrate the application of phosphorus-modified rare earth shape-selective zeolite adsorbents in gasoline desulfurization.

[0075] Using raw gasoline A and B in Table 1 as raw materials, the adsorption and catalytic conversion of raw gasoline raw materials in small fluidized bed reactors were fully contacted with adsorbents PZS-1 and PZS-2 respectively. The loading capacity of the adsorbent is 500 grams, and it is reduced for 60 minutes with hydrogen at a temperature of 360° C. and a hydrogen flow rate of 1.5 liters / hour before use. The reaction product, steam and the raw adsorbent mixture are separated in the settler, and the reaction product is separated to obtain gas products and liquid products, while the raw adsorbent is stripped of the hydrocarbon products adsorbed on the raw adsorbent mixture by steam. The stripped adsorbent is regenerated by contacting with heated air, and the regenerated catalyst mixture is recycled after cooling and hydrogen re...

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Abstract

The invention provides a sorbent used for reducing the content of sulfide in light hydrocarbon oil. According to weight percentage, the sorbent comprises 1-30% of phosphorus-modified rare earth shape-selective zeolite, 5-40% of active metal oxide and 30-94% of carrier; wherein, the carrier comprises alumina and zinc oxide; the rare earth shape-selective zeolite is modified by phosphorus and is pre-formed into porous heat-resistance solid grains together with carrier mixture; subsequently, the active metal oxide is led into the solid grains, thus preparing the sorbent; the light hydrocarbon oil raw material containing the sulfur and hydrogen donor enter a reactor filled with the sorbent; the materials are separated after reaction; the reaction products are sent to a subsequent separation system so that the product is separated; the sorbent to be regenerated after reaction is stripped, burned and regenerated; and the regenerated sorbent is reduced by the hydrogen donor and subsequently returns to the reactor so as to be circularly used. The sorbent realizes that the sulfide of light hydrocarbon oil is deeply removed, and meanwhile, the octane number of the outcome gasoline is higher, while the benzene content is lower and the strength is higher.

Description

technical field [0001] The invention belongs to an adsorbent for reducing sulfur content in light petroleum hydrocarbons and its preparation and application. Background technique [0002] As people pay more and more attention to environmental protection, the restrictions on sulfur content in light hydrocarbon oil used as fuel are becoming more and more stringent. Taking gasoline as an example, the U.S. Environmental Protection Agency (EPA) stipulates that the sulfur limit is 30 μg / g (Tier II); Europe requires gasoline sulfur content to be less than 50 μg / g (Euro IV emission standard); China will gradually limit gasoline sulfur content With international standards. Therefore, the hydrocarbon oil must be deeply desulfurized to meet the requirements. [0003] At present, in addition to hydrogenation technology, the deep desulfurization method of oil products, the removal of sulfur compounds in fuel oil by adsorption method is also a very attractive technology in recent years....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G25/05
Inventor 徐莉谢朝钢许友好唐津莲杨萍华汪燮卿达志坚张久顺
Owner CHINA PETROLEUM & CHEM CORP
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