Desulphurization sorbent

An adsorbent and zeolite technology, applied in inorganic chemistry, refined hydrocarbon oil, petroleum industry, etc., can solve the problems of gasoline product octane loss and insufficient to achieve deep desulfurization, so as to improve gasoline octane number and adsorbent distribution Uniformity and good desulfurization activity

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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  • Desulphurization sorbent

Examples

Experimental program
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Effect test

preparation example Construction

[0048] The preparation of the adsorbent solid particles used in this embodiment is as follows:

[0049] The main raw materials of the carrier used in this embodiment are as follows:

[0050] C1 # 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.);

[0051] C2 # 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);

[0052] C3 # Carrier: 5 kilograms of pseudo-boehmite+4 kilograms of kaolin+2 kilograms of cumulated clay (solid content is 68% by weight, product of Hubei Mingliu Rectorite T...

Embodiment 1-3

[0062] Examples 1-3 illustrate the composition and preparation method of adsorbents containing rare earth zeolite mixtures.

[0063] 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.

[0064] Mix nickel chloride solution with S1 at room temperature # -C1 #Mix the solid particles, add ammonia water with a concentration of 3mol / L while stirring, keep 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 there is no acid ion A mixture of nickel hydroxide, P-RE-ZSM5, P-REY and alumina carrier material is prepared, and washed with water until there is no chloride ion. After drying at 100-200°C for at least 2 hours, then roasting at 500-800°C for at least 2 hours, cr...

Embodiment 4-5

[0073] Examples 4-5 illustrate the application of rare earth zeolite mixture adsorbents in gasoline desulfurization.

[0074] 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 ZYS-1 and ZYS-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 reduction. The test condition...

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Abstract

The invention discloses a desulfurization adsorbent, which comprises 1 to 30 weight percent of rare earth-zeolite mixture, 5 to 40 weight percent of active metal oxide and 30 to 94 weight percent of carrier, wherein the carrier comprises alumina and zinc oxide; the rare earth-zeolite mixture and a carrier mixture are preformed into porous heat-resistant solid particles, and then active metal ingredients are introduced on the solid particles to obtain the adsorbent; and a light hydrocarbon oil raw material containing sulfur and a hydrogen donor enter a reactor filled with the adsorbent, materials remained after the reaction are separated, a reaction product is sent into a subsequent separation system for product separation, a spent adsorbent after the reaction is steam-stripped and then is subject to coke-burning regeneration, and the regenerated adsorbent is reduced by the hydrogen donor and is returned to the reactor for cyclic use. The adsorbent realizes the deep removal of sulfide in light hydrocarbon oil, and the produced gasoline has higher octane number, lower benzene content, and higher strength at the same time.

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): B01J20/10B01J20/06B01J20/30C10G25/00
Inventor 许友好徐莉汪燮卿达志坚张久顺谢朝钢唐津莲
Owner CHINA PETROLEUM & CHEM CORP
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