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Sulfur alcohol oxidation catalyst, its preparing and use

A mercaptan oxidation and catalyst technology, applied in the direction of physical/chemical process catalysts, refining with oxygen-containing compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of difficult application, low activity stability, unrecorded Catalyst regeneration effect and other issues

Inactive Publication Date: 2007-06-13
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the catalyst activity stability (based on the mercaptan sulfur content after catalyst treatment is not more than 20ppm, the activity stability is only about 480h) is far lower than the liquid alkali system with metal cyanine as catalyst in industry; meanwhile, in CN1200958A Among them, the regeneration effect after catalyst deactivation is not recorded, so it is difficult to apply in industry

Method used

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preparation example Construction

[0017]The method for preparing the above-mentioned mercaptan oxidation catalyst of the present invention comprises: mixing and dissolving metal phthalocyanines with positive ion groups and metal phthalocyanines with negative ion groups in hydroxide solutions of alkali metals or alkaline earth metals or ammonia water Among them, sodium hydroxide solution or ammonia water is preferred, and then impregnated with porous material. Spray impregnation, equal volume impregnation or excess impregnation can be used. Wherein the porous material does not include the following substances: the general formula is xMO·yM' 2 o 3 A solid basic oxide, wherein M is a divalent metal selected from Mg, Ni, Zn, Cu, Fe, Co; M' is a trivalent metal selected from Al, Cr, Ga; x / y is 1 to 15 ; it is represented by the general formula M x M' y (OH) 2x+2y (X) y / n ·zH 2 The hydrotalcite-type layered dihydroxide of O is prepared by calcining at 300-750°C according to the conventional method, wherein X ...

Embodiment 1

[0028] This embodiment illustrates that the quaternary ammonium salt phthalocyanine cobalt CoPc[N(CH) used in the catalyst of the present invention 3 ) 3 I] 4 Synthesis, the synthesis is carried out with reference to the method reported in the document J.Mol.Catal., 1994, Vol.87, P161.

[0029] 0.15gCoPc(NH 4 ) 4 (Refer to the literature Polyhedron, 1987, 6: 1463 synthesis) dissolved in 50ml N, N-dimethylformamide (DMF), then add 1.0ml 2,6-lutidine and 20ml CH 3 I react. After 2 days, the reaction solution was poured into 300 ml of ether, and a precipitate was deposited. Filter and wash the precipitate with 200ml ether. Then, the precipitate was added to 500ml H 2 O, heated at 90°C for 1 h, filtered, and evaporated under reduced pressure to remove H 2 O. Recrystallize with DMF and ether to obtain dark blue quaternary cobalt phthalocyanine product.

Embodiment 2

[0031] This embodiment illustrates that tetrasulfonate sodium phthalocyanine cobalt CoPc (SO4) used in the catalyst of the present invention 3 Na) 4 Synthesis.

[0032] Slowly add 2.0g of cobalt phthalocyanine (CoPc) into 30g of 30% oleum (consisting of 20g of 50% oleum and 10g of 98% concentrated sulfuric acid) under ice-water bath with stirring, after the cobalt phthalocyanine is dissolved , reacted at 30-35°C for 48 hours, then added the above reaction solution dropwise to 200ml ice water for hydrolysis, filtered out the precipitate, dissolved and neutralized the above precipitate with NaOH aqueous solution, evaporated the water under reduced pressure, and then used 50ml methanol and 50ml Acetone recrystallization, with 200ml dehydrated alcohol washing, after drying, obtain tetrasulfonate sodium phthalocyanine cobalt CoPc (SO 3 Na) 4 (Characterized by elemental analysis and infrared spectroscopy).

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Abstract

The present invention provides a mercaptan oxidation catalyst. Said catalyst uses multiporous material as carrier, and uses metallophthalocyanine with positive ion group and metallophthalocyanine with negative ion group as active component. Said invention also provides a method for mercaptan oxidation, said method is characterized by that in the presence of oxygen gas and alkaline solution medium the hydrocarbon flow is contacted with the invented catalyst. Besides, said invention also provides the preparation method of said catalyst and its concrete steps.

Description

technical field [0001] The invention relates to a catalyst for mercaptan oxidation, in particular, a catalyst with a porous material as a carrier and positive and negative ion pair metal phthalocyanine as an active component. The invention also relates to a method for preparing the catalyst and a method for catalyzing the oxidation of mercaptans. Background technique [0002] Mercaptans are widely present in natural gas, liquefied petroleum gas, gasoline, kerosene, jet fuel, diesel and other hydrocarbon fluids. The presence of mercaptans can cause a variety of serious problems, such as bad odor, corrosion, etc. Therefore, it is very necessary to remove mercaptans from various process materials or fluids. Generally, the industrial process of converting mercaptans into disulfides by catalytic oxidation is called deodorization. A deodorization method commonly used in industry is the Merox catalytic oxidation process developed by UOP Company of the United States. The Merox c...

Claims

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Application Information

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IPC IPC(8): B01J31/18B01J31/22C10G27/10
Inventor 潘光成李涛吴明清陶志平张红霞董伟张小云
Owner CHINA PETROLEUM & CHEM CORP
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