CN113336216A - Catalytic desulfurization method in petroleum coke calcining furnace - Google Patents

Abstract

The invention provides a method for catalytic desulfurization in a petroleum coke calcining furnace, which comprises the steps that a catalytic desulfurizing agent is adjusted along with the sulfur content of petroleum coke, a PerkinElmer thermogravimetric analyzer tracks the temperature section of catalytic desulfurization escaping in advance, and a desulfurized compound structure is determined by TG-MS, so that the desulfurization rate of calcined coke is increased by more than 50%, and the obtained calcined coke has low volatile component and high true density; meanwhile, the flue gas desulfurization rate of the calcining furnace reaches more than 98 percent.

Description

Catalytic desulfurization method in petroleum coke calcining furnace

The technical field is as follows:

the invention relates to a catalytic desulfurization method in a petroleum coke calcining furnace.

Background art:

the sulfur content of petroleum coke is high, which affects the quality of calcined coke, and for graphite products used for producing anode materials for aluminum electrolysis, graphite electrodes produced by petroleum coke with high sulfur content can generate a gas expansion phenomenon in the graphitization process, which is easy to cause product cracks. When the graphite electrode with higher sulfur content is used for aluminum smelting, the consumption of the aluminum electrode per ton is increased. At present, the sulfur content of petroleum coke produced by high-sulfur crude oil or imported high-sulfur crude oil used in oil refineries reaches 3.6-4.5%, and the sulfur content of petroleum coke produced by high-sulfur crude oil or imported high-sulfur crude oil even reaches 7.0%. The calcination temperature in the furnace is about 1200-1300 ℃, the desulfurization effect before and after calcination is usually not more than 20% (partial organic sulfur can be removed), the desulfurization effect can be more obvious only by increasing the calcination temperature to about 1450 ℃, and partial sulfide can be removed even at the higher graphitization temperature of 1700-2300 ℃. To achieve low temperature calcination at 1000 ℃, the invention patent (application No.: 201810879133.9) disclosed by medium carbon energy (Shandong) company 2018.1207: after the petroleum coke is subjected to special unpublished pretreatment, inorganic sulfur is removed by adopting a permanent magnet iron removal method, and the petroleum coke is introduced into a pot-type calcining furnace, so that the sulfur content of the calcined coke is finally reduced to 0.276-0.282%. The invention patent of published Japanese patent application No. 2013.5.8 of northeast university (application No. 201110336269.3) is a method for removing sulfur components in petroleum coke by using a sodium hydroxide/potash melting method, and although the desulfurization rate of the petroleum coke reaches more than 98 percent and the sulfur content of the petroleum coke is as low as 0.1 percent, soluble sulfur components need to be filtered when the petroleum coke is heated to 400-600 ℃, and alkali/coke is 1: 1-4: 1, which is only a method staying in a laboratory exploration stage. CN10184977A a method for removing sulfur in petroleum coke and a desulfurizer thereof, relates to a method for controlling mixed acid with fixed proportion, soaking for a period of time, then washing and drying, and has the problems of low cost, large water consumption in the process and the like.

Disclosure of Invention

Aiming at the defects of the existing petroleum coke desulfurization, the invention provides a catalytic desulfurization method for a calcining furnace, wherein the catalytic desulfurization agent capable of forming coordination and containing cyano is prepared from cyanoguanidine, calcium cyanide, calcium xanthohumate, isothiocyanate and cyanamide humate in a mass ratio of 0.1:0.2:0.2:0.3: 0.2; or a catalytic desulfurizer containing nitrile groups, which is prepared from acrylonitrile, polyacrylonitrile, benzonitrile, and phenylacetonitrile-fulvic acid-isobutyronitrile according to the mass percentage of 0.35:0.15:0.15:0.20: 0.15; the acyl, the amide group, the N-benzoyl, the caprolactam and the humic acid sulfenamide are regulated according to the mass percentage of 0.15:0.25:0.1:0.3:0.2 and the mass percentage of 1.0-5.0 percent along with the change of the sulfur content of the petroleum coke according to the law of mass action.

And tracking by the PerkinElmer thermogravimetric analyzer, synchronizing with non-catalytic pyrolysis of the high-sulfur petroleum coke at the same temperature, and comparing the temperature of the catalytic desulfurization reduction calciner desulfurization with the temperature of 100-950 ℃ and the weight loss rate.

The structure of the petroleum coke desulfurization compound determined by TG-MS of German Netzsch company compares aliphatic hydrocarbon sulfide, aromatic sulfide, fused ring aromatic hydrocarbon sulfide and the like. There are mercaptans, thioethers, thiophenethiols, sulfonic acids, and sulfoxides, sulfones, SO2 converted from iron sulfates, etc. .

The desulfurization rate of the petroleum coke after calcination is increased to more than 70 percent from the original 15-20 percent, so that the sulfur content of the petroleum coke is reduced to less than 2.0 percent. The determination method is an Eschka sulfur determination method or a high-temperature combustion rapid sulfur determination method.

The volatile component of the calcined coke is 0.2 to 0.5 percent, the true density is 2.01 to 2.07, and the flue gas desulfurization rate of the calcining furnace is 95 to 99 percent

Drawings

FIG. 1 is a graph of non-catalytic pyrolysis of petroleum coke

FIG. 2 is a graph of catalytic pyrolysis of petroleum coke

The specific implementation method comprises the following steps:

example one

Taking petroleum coke with 4.6 percent of sulfur content, carrying out non-catalytic pyrolysis at 100-950 ℃, wherein the weight loss rate is 150-300 ℃ and 1.835 percent as the tracking chart of a PerkinElmer thermogravimetric analyzer (figure 1), and the weight loss rate is compared and determined in the PerkinElmer thermogravimetric analyzer; 320 ℃ and 650 ℃, weight loss rate of 6.353%; 700-940 deg.c and weight loss rate of 2.006%.

Example two

Petroleum coke with a sulfur content of 4.6 percent is taken, 2.3 percent of catalytic desulfurizer which can form ligand and contains cyano, nitrile, acyl and amido is regulated, catalytic pyrolysis is carried out at 100-950 ℃, the weight loss rate is 3.187 percent as a tracing graph of a PerkinElmer thermogravimetric analyzer (figure 2), the temperature is 250-300 ℃; 320 ℃ and 520 ℃, and the weight loss rate is 6.595%; 530 ℃ to 650 ℃, weight loss rate 7.362%, 700 ℃ and 950, no weight loss rate was detected.

EXAMPLE III

Taking petroleum coke with the sulfur content of 4.6 percent, adjusting a catalytic desulfurizer which can form a ligand and contains an amido group, benzoyl, N-benzoyl, caprolactam and humic acid amide according to the mass percent of 0.15:0.25:0.1:0.3:0.2 and the proportion of the total content of the catalyst to the petroleum coke of 2.3 percent, carrying out catalytic pyrolysis in a petroleum coke calcining furnace at 1100 ℃, measuring by adopting a Geranium Huaneng WDL-HN800 high-temperature combustion rapid sulfur detector after 48 hours to reduce the sulfur content of the petroleum coke to be below 2.0 percent, reducing the volatile content of the calcined coke to be 0.20 percent and the real density to be 2.05 percent, and simultaneously ensuring the flue gas desulfurization rate of the calcining furnace to be 95.0 percent

Example four

Taking petroleum coke with the sulfur content of 4.6 percent, adjusting a nitrile-group-containing catalytic desulfurizing agent capable of forming a ligand group, containing a nitrile group, acrylonitrile, polyacrylonitrile, benzonitrile and phenylacetonitrile-fulvic acid isobutyronitrile according to the mass percent of 0.35:0.15:0.15:0.20:0.15, wherein the total content of the catalyst and the petroleum coke form a proportion of 2.5 percent, carrying out catalytic pyrolysis at 1100 ℃, measuring by adopting a high-temperature combustion rapid sulfur detector of Erythrochan George WDL-HN800 percent after 72 hours, reducing the sulfur content of the petroleum coke to below 1.0 percent, reducing the volatile component of the calcined coke to 0.20 percent and the true density to 2.05 percent, and simultaneously ensuring the flue gas desulfurization rate of a calcining furnace to be 98.0

EXAMPLE five

The method comprises the steps of taking petroleum coke with the sulfur content of 4.60%, adjusting a cyano-containing catalytic desulfurizer capable of forming a ligand, carrying out catalytic pyrolysis at 1000 ℃ by using cyanoguanidine, calcium cyanide, calcium cyanamide fulvate, isothiocyanate and cyanamide humate in a mass percentage of 0.1:0.2:0.2:0.3:0.2 and a ratio of 2.00% of the total content of a catalyst to the petroleum coke, measuring the product by using a high-temperature combustion rapid sulfur detector of Gecko Huanen WDL-HN800 after 60 hours to reduce the sulfur content of the petroleum coke to below 1.1%, reducing the volatile component of calcined coke to 0.20%, and ensuring the true density to 2.05, and simultaneously ensuring the flue gas desulfurization rate of a calcining furnace to be 97.0%.

Claims (6)

1. A catalytic desulfurization method in a petroleum coke calcining furnace is characterized by comprising the following steps: the catalytic desulfurizer is adjusted along with the sulfur content of petroleum coke, a PerkinElmer thermogravimetric analyzer tracks and compares the catalytic desulfurization to reduce the desulfurization temperature section and the weight loss rate of the calcining furnace, and a desulfurization compound composition structure determined by TG-MS comprises the calcined coke desulfurization rate, the calcined coke volatile component, the true density and the calcining furnace flue gas desulfurization rate.

2. The process as claimed in claim 1, wherein the desulfurizing catalyst containing cyano group, nitrile group, acyl group and amide group is adjusted to 1.6-3.0% according to the law of mass action as the sulfur content in petroleum coke changes from 3.2-6.0%.

3. The method of claim 1 wherein the temperature step of reducing calciner desulfurization is from 100 ℃ to 900 ℃ as tracked and compared by a Perkinelmer thermogravimetric analyzer.

4. The process as claimed in claim 1, wherein the desulfurization compound structure is defined by TG-MS from Netzsch, Germany, and includes mercaptans, sulfides, thiophenethines, sulfonic acids, and sulfoxides, sulfones, SO2 converted from iron sulfate and sulfates. .

5. Claim 1 wherein the desulfurization rate of the calcined coke is increased from 15% to 20% to more than 50%.

6. The process as in claim 1, wherein the calcined coke has a volatile content of 0.2-0.5%, a true density of 2.01-2.05, and a calciner flue gas desulfurization rate of 95-98%.

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