CN101972678A - Preloaded composite desulfuration catalyst and preparation method thereof - Google Patents

Abstract

The invention relates to a preloaded composite desulfuration catalyst and a preparation method thereof. The preparation method comprises the following steps of: dissolving NaOH in deionized water to prepare aqueous solution of NaOH; adding cobalt sulfonated phthalocyanine into the aqueous solution of NaOH and stirring uniformly; adding activated carbon for dipping; drying and sieving at normal temperature; and packing to obtain the preloaded composite desulfuration catalyst product. The problems that bipolymer is easily formed and catalytic active sites are reduced when the cobalt sulfonated phthalocyanine is independently used are solved, phase transfer is inhibited, and catalytic efficiency is improved; meanwhile, the product is easy to recover and regenerate, can be recycled and has obvious economic benefit. The catalyst prepared by the method has high catalytic activity, and can make treated oil gas have the mercaptan content of below 10ppm; and the copper strip corrosion test is qualified and a doctor test is passed.

Description

Preload composite desulfate catalyst and preparation method thereof

Technical field:

The present invention relates to a kind of oil refining and chemical industry purification techniques, especially the preparation method of a kind of desulfurizing agent in the desulfurizing and purifying technology and this desulfurizing agent.

Background technology:

The desulfurizing and purifying technology is widely used in practicing oil and chemical engineering industry, the desulfurizing and purifying technology is different because of the phase of the size of sulfide species and molecular weight and medium, if medium is liquid, as oil product, sulfide is organic sulfur compound, general application hydrodesulfurization, by hydrogenation, make organic sulfur be converted into the hydrogen sulfide that molecular weight is less, boiling point is lower, the difference of the boiling point of sulfide and medium is widened, by stripping, sulphur is removed.If the sulfide molecules amount is little, boiling point is low, and medium is a gas phase, and sulfide and medium belong to gas phase together, and general the employing absorbs or adsorption desulfurize, absorbs desulfurization and divides dry method and wet method again.Zinc oxide desulfurizer belongs to dry-desulphurizer, by hydrogen sulfide, cos, the little molecule mercaptan in the conversion absorbing and removing gas.Sulfide in the gas and solid oxidation zinc reactive desulfurizing agent generate zinc sulphide and harmless micromolecular compound, and zinc sulphide is still stayed in the desulfurizing agent, belongs to gas-solid heterogeneous reaction.At first from the desulfurizing agent surface, inwardly layer depth is gone into then in reaction, and surface reaction is fast, but the duration is short.Internal layer reaction resistance is big, and reaction is slow, but longer duration, desulphurization reaction mainly carries out at internal layer.For reducing the reaction resistance, desulfurizing agent wants hole system flourishing, and specific surface is big, and internal layer is thin.For overcoming the resistance that the inside layer depth of reaction is gone into, improve reaction temperature, according to the serviceability temperature of desulfurizing agent, desulfurizing agent divides high temperature desulfuration agent, middle low-temp desulfurization agent and ambient temperature desulfuration agent.The serviceability temperature of high temperature desulfuration agent＞350 ℃, the power that overcomes resistance is big, and specific surface can be smaller, is about 40m ²/ g, the serviceability temperature of middle low-temp desulfurization agent is at 50 ℃-350 ℃, and specific surface should be greatly, the serviceability temperature of low-temp desulfurization agent＜50 ℃, specific surface should be bigger.In order to increase the specific surface of desulfurizing agent, CN93111222.2 discloses a kind of predecessor that uses zinc carbonate and basic zinc carbonate to do zinc oxide, and these materials play blowing agent simultaneously.CN01144140.2 discloses and has a kind ofly made adhesive with clay, plays the permeability promoter effect simultaneously, because clay hole system is flourishing inadequately, the specific surface of the desulfurizing agent of preparation also has only 50m ²/ g.

Metal phthalocyanine compound at first is widely used in coating, printing and textile industry as a kind of colouring agent.Because it has good heat-resisting, fast light photograph, acid and alkali-resistance stability etc., can be used as tens of kinds of organic reactions of catalyst, the reduction reaction that comprises hydrogen exchange reaction, hydrogenation reaction, nitrogen oxide and acetylene, the decomposition reaction of peroxide, hydrogen peroxide and formic acid, ammonia synthesis reaction, carboxyl removes reaction, the hydroxylating of aromatic hydrocarbons, dehydrogenation reaction, electrochemical reaction and oxidation reaction etc. are a kind of good catalyst.But metal phthalocyanine easily forms the dimer even the polymer of non-activity in solution, the formation of polymer will reduce the active site of axial coordination, thereby causes catalytic efficiency to reduce.In addition, sulfonated phthalocyanine cobalt directly easily causes phase transfer as catalyst, has limited its application, and catalyst is difficult for reclaiming, loss is serious.

Summary of the invention:

Purpose of the present invention just is at above-mentioned the deficiencies in the prior art, and a kind of preload composite desulfate catalyst is provided;

Another object of the present invention provides a kind of preload composite desulfate catalyst preparation method

The objective of the invention is to be achieved through the following technical solutions:

Preload composite desulfate catalyst solvent and mass percent are:

NaOH 5.6％-8％

Deionized water 20%-32%

Sulfonated phthalocyanine cobalt 0.4%-1.0%

Active carbon 59%-74%

2. according to the described preload composite desulfate catalyst of claim 1 preparation method, it is characterized in that, comprise following order and step:

A, usefulness 20%-32% deionized water dissolving 5.6%-8%NaOH make the NaOH aqueous solution;

B, the 0.4%-1.0% sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 59%-74% active carbon dipping 20-30min;

D, normal temperature are dry down, screening;

E, pack preload composite desulfate catalyst product.

Beneficial effect: be synthetic sulfonated phthalocyanine cobalt to be carried on make the preload composite desulfate catalyst on the active carbon.When both having solved independent use sulfonated phthalocyanine cobalt, it easily forms the problem that dimer, catalytic activity point reduce, and has suppressed phase transfer again, has improved catalytic efficiency; Simultaneously product easily reclaims, regenerates, and can realize recyclingly, has obvious economic benefit.The catalyst that this method makes, the catalytic activity height can make and handle that mercaptans content is less than 10ppm in the oil gas of back, and copper corrosion is qualified, passes through the doctor test.

The specific embodiment:

Connect below with embodiment and be described in further detail:

Preload composite desulfate catalyst solvent and mass percent are:

NaOH 5.6％-8％

Deionized water 20%-32%

Sulfonated phthalocyanine cobalt 0.4%-1.0%

Active carbon 59%-74%

Preload composite desulfate catalyst preparation method comprises following order and step:

A, usefulness 20%-32% deionized water dissolving 5.6%-8%NaOH make the NaOH aqueous solution;

B, the 0.4%-1.0% sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 59%-74% active carbon dipping 20-30min;

D, normal temperature are dry down, screening;

E, pack preload composite desulfate catalyst product.

Embodiment 1:

A, get 200ml deionized water dissolving 56gNaOH, make the NaOH aqueous solution;

B, the 4g sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 590g active carbon dipping 20min;

D, normal temperature are dry down, broken particle is removed in screening;

E, pack preload composite desulfate catalyst product.

Embodiment 2:

A, get 250ml ionized water dissolving 65gNaOH, make the NaOH aqueous solution;

B, the 6g sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 660g active carbon dipping 25min;

D, normal temperature are dry down, broken particle is removed in screening;

E, pack preload composite desulfate catalyst product.

Embodiment 3:

A, get 300ml ionized water dissolving 70gNaOH, make the NaOH aqueous solution;

B, the 8g sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 700g active carbon dipping 28min;

D, normal temperature are dry down, broken particle is removed in screening;

E, pack preload composite desulfate catalyst product.

Embodiment 4:

A, get 320ml ionized water dissolving 80gNaOH, make the NaOH aqueous solution;

B, the 10g sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 740g active carbon dipping 30min;

D, normal temperature are dry down, broken particle is removed in screening;

E, pack preload composite desulfate catalyst product.

Claims (2)

1. a preload composite desulfate catalyst is characterized in that, solvent and mass percent are:

NaOH 5.6％-8％

Deionized water 20%-32%

Sulfonated phthalocyanine cobalt 0.4%-1.0%

Active carbon 59%-74%

2. according to the described preload composite desulfate catalyst of claim 1 preparation method, it is characterized in that, comprise following order and step:

A, usefulness 20%-32% deionized water dissolving 5.6%-8%NaOH make the NaOH aqueous solution;

B, the 0.4%-1.0% sulfonated phthalocyanine cobalt is joined in the NaOH aqueous solution, stir;

C, adding 59%-74% active carbon dipping 20-30min;

D, normal temperature are dry down, screening;

E, pack preload composite desulfate catalyst product.