CN112646625A

CN112646625A - Sludge briquette composition and preparation method thereof

Info

Publication number: CN112646625A
Application number: CN201910966443.9A
Authority: CN
Inventors: 杨豫森; 崔华; 陈辉
Original assignee: Hep Energy And Environment Technology Co ltd
Current assignee: Hep Energy And Environment Technology Co ltd
Priority date: 2019-10-12
Filing date: 2019-10-12
Publication date: 2021-04-13

Abstract

The invention provides a sludge briquette composition and a preparation method thereof, wherein the sludge briquette composition comprises sludge, coal dust, a desulfurizer, an adhesive and a catalyst, and the adhesive is selected from at least one of oil asphalt and tar residue. The preparation method comprises the following steps: selecting 20-60 parts of sludge, 30-70 parts of coal powder, 1-10 parts of desulfurizer and 1-10 parts of adhesive according to the calculated proportion; adding sludge and an adhesive into the coal dust, and uniformly stirring for later use; adding a desulfurizer into the coal dust, and uniformly stirring for later use; after homogenizing and curing, the materials are mixed uniformly and fully contacted, and then the mixture is put into a molding device for hot press molding. The method not only realizes effective recycling of resources and changes waste into valuable, but also ensures that indexes such as flue gas emission, sulfur dioxide emission and the like after burning of the semi-coke finally obtained can meet the environmental protection requirement, reduces environmental pollution, and can obtain a clean type coal product with high calorific value after a low-temperature dry distillation process of the type coal product.

Description

Sludge briquette composition and preparation method thereof

Technical Field

The invention relates to the technical field of clean briquette preparation, in particular to a sludge briquette composition and a preparation method thereof.

Background

The energy structure of China is expressed as rich coal, lean oil and little gas, compared with petroleum, natural gas and other energy resources, the coal resources of China are rich and are the largest coal producing and consuming countries in the world, and the yield accounts for 37 percent of the total yield of coal in the world. The proportion of coal in the primary energy structure of China is about 70%, and the situation is expected not to change fundamentally in the next decades. However, at present, about 80% of coal in China generates electric energy in a direct combustion mode, so that the efficiency is low, resources are wasted, and the environment is polluted, so that the comprehensive utilization of the coal is sought, and the improvement of the added value of the coal becomes a hotspot in the coal chemical industry in recent years.

On the other hand, sludge treatment is a problem in social development. The sludge is divided into industrial sludge produced by oil gas and industry and municipal sludge produced by municipal sewage treatment industry according to the production source.

The oily sludge refers to sludge mixed with heavy oil such as crude oil, oil residue, various finished oils, etc. The natural world does not inherently have oily sludge, but because of various industries related to finished oil and crude oil, such as oil field exploitation, petroleum smelting, use, storage, transportation, civil groups, individuals and the like, the crude oil and the finished oil leak out through running, dripping, overflowing and leaking due to various accident operations and equipment problems and are mixed with water, soil and the like to form a mixture containing oil, water, soil and even other pollutants. Oily sludge becomes a treatment problem in the oil and gas exploitation industry.

(1) Production of crude oil produces oily sludge:

in the land polluted by crude oil, a large amount of oily sludge covers the oily sludge generated in the process of surface crude oil exploitation, and the oily sludge is mainly from a ground treatment system, wherein the oily sludge generated in the process of oil extraction sewage treatment, flocs formed by a water purifying agent added in sewage purification treatment, equipment and pipeline corrosion products, dirt, bacteria (corpses) and the like form the oily sludge. The oily sludge generally has the characteristics of high oil content, high viscosity, fine particles, difficult dehydration and the like, and not only influences the quality of the exported crude oil, but also causes the water quality of injected water and the discharged sewage to reach the standard.

(2) Oil-containing sludge produced in oil field gathering and transportation process

The oily sludge produced in the oil field gathering and transportation process mainly comes from oil tanks, settling tanks, sewage tanks, oil separation tank bottom mud of transfer stations and combination stations, oil sand and oil sludge removed by oil-containing water treatment facilities, light hydrocarbon processing plants and natural gas purification devices in refineries, and ground crude oil and oily sludge produced by drilling, oil field operation and pipeline perforation. When the oil product storage tank is used for storing oil products, a small amount of mechanical impurities, sand grains, soil, heavy metal salts, paraffin, asphaltene and other heavy oily components in the oil products are deposited at the bottom of the oil tank to form tank bottom oil sludge. The oily sludge has complex components, contains a large amount of aged crude oil, wax, asphaltene, colloid, solid suspension, bacteria, salts, acidic gas, corrosion products and the like, and is also added with a large amount of water treatment agents such as a coagulant, a corrosion inhibitor, a scale inhibitor, a bactericide and the like in the sewage treatment process and mixed in the oily sludge.

In 3-6 years of regular cleaning of the oil tank, the oil-containing sludge at the tank bottom accounts for about 1 percent of the tank volume. Tank bottom oily sludge is characterized by extremely high hydrocarbon (oil) content, and typical oil tank bottom sludge analysis results show that about 25% of the tank bottom sludge is water, 5% of inorganic sediment such as silt, about 70% of the tank bottom sludge is hydrocarbon, 7.8% of asphaltene, 6% of paraffin and 4.8% of sludge ash content are contained in the tank bottom oily sludge.

(3) Oily sludge generated in a sewage treatment plant of an oil refinery: the oily sludge of the sewage treatment field of the oil refinery mainly comes from oil separation tank bottom mud, flotation tank scum, crude oil tank bottom mud and the like, commonly called as 'three-mud', and the oily sludge has different compositions, usually has the oil content of between 10 and 50 percent and the water content of between 40 and 90 percent and is accompanied by a certain amount of solid.

(4) Contaminated soil caused by oil used in industries such as iron and steel smelting

(5) In offshore oil field exploitation, shipbuilding and ship repair, coastlines and river margins polluted by heavy oil hydrocarbons are used, the seabed contains oil sludge, and water bodies, surface oil sludge and the like caused by oil product leakage caused by oil tank truck and ship accidents are adopted.

In addition, in the oil and fat refining process, activated clay accounting for 2 to 3 percent of the weight of oil is generally used, and the decolorized clay loses activity to become waste clay which is a large amount of solid waste. The conventional normal treatment mode of the waste white soil is to discard the waste white soil to a landfill site; however, the unsaturated oils contained in the spent bleaching clay are rapidly oxidized to the self-ignition point to generate odor and risk of fire, and for the reasons mentioned above, the spent bleaching clay is no longer allowed to be discarded in landfills or public disposal sites in many countries. The main components of the waste argil are argil, colloid, asphaltene, polycyclic aromatic hydrocarbon and about 30% of oil, and if the waste argil cannot be recycled well, environmental pollution and resource waste can be caused.

The sludge causes great pollution to the environment, and the sludge is treated by high-temperature pyrolysis in the prior art, and meanwhile, effective components such as oil, gas and the like are extracted from the sludge and subjected to harmless treatment. For example, patent publication No. CN103130390B discloses a method and a process for treating oily sludge, wherein, a pH regulator is added into oily sludge with water content more than 70% to regulate the pH value to 7-8, then an inorganic flocculant and an organic flocculant are added to carry out dehydration treatment, the dehydrated oily sludge enters a pyrolysis device for pyrolysis, and gas generated by pyrolysis enters a gas recovery device for recycling; the produced oil and water enter an oil-water separation device for oil-water separation, the separated oil enters an oil storage tank for recycling, and the separated water enters a sewage treatment device or an oil field water treatment system; adding an ignition agent, a combustion improver, a binder and a desulfurizer into the pyrolysis excess sludge, and enabling the pyrolysis excess sludge to enter a fuel preparation device to prepare fuel for utilization. Although the technical problem of oily sludge treatment in oil fields and refining enterprises is solved to a certain extent by the prior art, the aims of effective recycling of resources, energy conservation, emission reduction and environmental protection are fulfilled. However, the pyrolysis process is high in temperature and energy consumption, and requires a very complicated treatment system, which is not favorable for recycling a large amount of sludge, thereby causing resource waste.

In addition, the preparation of the briquette adhesive in the prior art is complex and the cost is higher. For example, patent publication No. CN108517232A discloses a briquette binder prepared from the following raw materials: 5-8 parts of formaldehyde, 14-16 parts of humic acid, 3-5 parts of ethylene oxide, 7-9 parts of calcium hydroxide, 5-10 parts of sodium hydroxide, 3-5 parts of industrial salt, 3-5 parts of zeolite powder, 9-12 parts of oxalic acid, 18-25 parts of sodium silicate, 3-5 parts of starch and 15-25 parts of water. Therefore, the briquette adhesive has complex components and higher preparation cost.

A prior art patent publication No. CN101560426A discloses a briquette additive, which is composed of the following raw materials by weight percent: 0.7-1.4% of magnesium oxide, 4-7% of potassium permanganate, 1-3% of paraffin, 2-6% of potassium chlorate, 2-6% of potassium nitrate, 2-6% of sodium nitrate, 3-7% of manganese dioxide, 0.8-2% of calcium carbonate, 0.5-2% of cobalt chloride and the balance of sodium chloride. Although the content of sulfur in tail gas generated by burning the briquette is reduced to a certain extent in the prior art, the tail gas generated by burning the briquette still contains a large amount of other harmful gases, so that the environmental pollution is serious.

Disclosure of Invention

In view of the above, the invention aims to provide a sludge briquette composition and a preparation method thereof, so as to solve the problems that in the prior art, the sludge treatment mode is complex, resource waste is easily caused, and the binder cost is high in the briquette preparation process.

In order to achieve the purpose, the technical scheme of the invention is realized as follows:

a sludge briquette composition comprises sludge, coal dust, a desulfurizing agent, an adhesive and a catalyst, wherein the adhesive is selected from at least one of oil asphalt and tar residue.

Further, the sludge comprises at least one of oil sludge, municipal sludge, waste activated clay and slag or dust fly ash of a power station boiler.

Further, the oil sludge is selected from oil sludge generated in the crude oil exploitation process, oil sludge generated in the oil field gathering and transportation process, oil sludge generated in a sewage treatment field of an oil refinery, polluted soil caused by oil used in the steel smelting industry, oil sludge generated in the offshore oil field exploitation, a coastline and river margin polluted by heavy oil hydrocarbons used for shipbuilding and ship repairing, water body generated by the oil sludge at the bottom of the sea and oil leakage caused by oil tanker and ship accidents, and surface oil sludge.

Further, the sludge briquette coal composition comprises the following components in parts by mass: 20-60 parts of sludge, 30-70 parts of coal powder, 0.5-10 parts of desulfurizer, 0-10 parts of adhesive and 0-10 parts of catalyst.

Further, the sludge briquette coal composition comprises the following components in parts by mass: the composite material comprises 20-60 parts of oil sludge, 30-70 parts of coal powder, 1-10 parts of a desulfurizer and 0-10 parts of a catalyst, wherein an oil-containing component in the oil sludge is used as an adhesive.

Further, the sludge briquette coal composition comprises the following components in parts by mass: 20-60 parts of municipal sludge, 30-70 parts of pulverized coal, 1-10 parts of an adhesive, 1-10 parts of a desulfurizer and 0-10 parts of a catalyst.

Further, the sludge briquette coal composition comprises the following components in parts by mass: the composite material comprises 20-60 parts of waste active white soil, 30-70 parts of coal powder, 1-10 parts of an adhesive, 1-10 parts of a desulfurizer and 0-10 parts of a catalyst.

Further, the sludge briquette coal composition comprises the following components in parts by mass: 20-60 parts of slag discharging or dust removing fly ash of a power station boiler, 40-60 parts of coal powder, 1-10 parts of an adhesive, 1-10 parts of a desulfurizer and 0-10 parts of a catalyst.

Further, the desulfurizer is divided into a sulfur-fixing desulfurizer and a composite desulfurizer, the composite desulfurizer can also be selected from composite desulfurizer prepared by synthesis process, and the composite desulfurizer comprises the following chemical components: 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 5-15 parts of cobalt chloride, 10-30 parts of calcium carbonate, 10-30 parts of wood vinegar and 1-10 parts of zinc oxide.

A preparation method of a sludge briquette composition comprises the following steps:

(1) selecting 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 5-15 parts of cobalt chloride, 10-30 parts of calcium carbonate and 10-30 parts of pyroligneous acid according to the calculated proportion, mixing the materials, and uniformly stirring the mixture to obtain a composite desulfurizer for later use;

(2) selecting 20-60 parts of sludge, 30-70 parts of coal powder, 0.5-10 parts of desulfurizer, 0-10 parts of adhesive and 0-10 parts of catalyst according to the calculated proportion;

adding sludge and an adhesive into the coal dust, and uniformly stirring for later use;

adding desulfurizer powder and catalyst powder into the mixture;

after homogenizing and curing, the materials are mixed uniformly and fully contacted, and then the mixture is put into a molding device for hot press molding.

Compared with the prior art, the sludge briquette composition has the following advantages:

compared with the mode of treating sludge by using a pyrolysis process in the prior art, the method has the advantages of no need of high temperature and less energy consumption, not only realizes effective recycling of resources and changes waste into valuable, but also can ensure that indexes such as flue gas emission, sulfur dioxide emission and the like after burning of the finally obtained semi-coke can meet the environmental protection requirement, reduce environmental pollution, can obtain a high-calorific-value clean carbon product after low-temperature dry distillation process of the coal product, can completely replace natural gas, and has wide application prospect in civil heating and industrial fuel.

The oil sludge, the oil asphalt or the tar residue is used as an adhesive to replace a common briquette adhesive in the prior art, so that raw materials are saved, and the qualified clean briquette with molding strength, water resistance and unnatural properties reaching the standard is manufactured. In the clean coal low-temperature dry distillation process, oil, gas, volatile matters and water in oil sludge, waste activated clay and municipal sludge are effectively recovered and are used for burning and heat supplementing of a dry distillation furnace or feeding the dry distillation furnace into a power station boiler for afterburning; pyrolyzing and gasifying harmful pollutants in the oil sludge, the waste activated clay and the municipal sludge, and performing harmless treatment in incineration or power station boiler flue gas treatment equipment; the effective utilization of the boiler ash of the power station is realized, and the benefit of the thermal power plant is increased.

Detailed Description

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The descriptions of "first", "second", etc. mentioned in the embodiments of the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicit ly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of the technical solutions should not be considered to exist, and is not within the protection scope of the present invention.

The present invention will be described in detail with reference to examples.

The invention provides a sludge briquette composition which comprises the following components in parts by mass: 20-60 parts of sludge, 30-70 parts of coal powder, 0.5-10 parts of desulfurizer, 0-10 parts of adhesive and 0-10 parts of catalyst.

The sludge comprises one or more of oil sludge, municipal sludge, waste activated clay and power station boiler slag discharge or dust removal fly ash, the oil sludge is selected from oil sludge generated in the crude oil exploitation process, oil-containing sludge generated in the oil field gathering and transportation process, oil-containing sludge generated in a sewage treatment field of an oil refinery, polluted soil caused by oil used in industries such as steel smelting and the like, and offshore oil field exploitation, coastline and river flow margins polluted by heavy oil hydrocarbons are used for shipbuilding and repairing, the oil-containing sludge on the seabed, water caused by oil leakage caused by oil tank truck accidents, oil-containing sludge on the surface of the water, and the like, and the sludge of different types can be recovered, so that the resource recovery utilization rate is improved.

The desulfurizer is used for absorbing the generated sulfur dioxide and reducing the content of the sulfur dioxide in the briquette product. Generally, the desulfurizing agent is classified into a sulfur-fixing type desulfurizing agent and a composite desulfurizing agent, wherein the sulfur-fixing type desulfurizing agent is at least one selected from calcium oxide, calcium hydroxide, metal oxide, metal hydroxide, basic oxide, basic hydroxide, carbonate, or a salt of a weak acid that is less acidic than sulfuric acid. The sulfur in the coal powder is oxidized into sulfur dioxide by the desulfurizer and the sulfur trioxide is combined with the desulfurizer to react, so that the sulfur content in the briquette coal product is reduced.

Further, the compound desulfurizing agent can be a compound I desulfurizing agent or a compound II desulfurizing agent prepared by a synthesis process, and the compound I desulfurizing agent comprises the following chemical components: 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 10-30 parts of calcium carbonate, 5-15 parts of cobalt chloride and 10-30 parts of wood vinegar. The magnesium oxide can effectively reduce the content of sulfur dioxide in the combustion products of the molded coal, the potassium permanganate reacts to generate oxygen, the combustion supporting effect is achieved, the cobalt chloride material can strongly decompose, catalyze and fission raw coal during combustion, and promote the coal to form loose shapes in the combustion to help the combustion and the exertion of carbon, in addition, the wood vinegar and the calcium carbonate are matched, the content of harmful gas sulfur dioxide in tail gas can be reduced, the emission of nitrogen oxide can be effectively reduced, and the semi-coke product obtained after the molded coal is subjected to the low-temperature dry distillation process is cleaner.

The compound II desulfurizer comprises the following chemical components: 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 10-15 parts of cobalt chloride, 10-30 parts of calcium carbonate, 10-30 parts of wood vinegar and 1-10 parts of zinc oxide.

The adhesive is oily sludge such as oil sludge, oil asphalt or tar residue, and the like, and because the oil sludge in certain areas contains a large amount of clay components due to underground oil layers and soil components, the oil sludge has certain viscosity and can replace the conventional coal briquette adhesive, and the oil sludge contains a certain amount of oil components and also has a certain combustion assisting effect, so that the oily sludge is used for replacing the conventional coal briquette adhesive, the harmless treatment of the sludge and the oil sludge is realized, and the combustibility of the fuel coal briquette can be effectively improved.

The catalyst comprises the following components: 30-60 parts of laterite-nickel ore, 20-40 parts of calcium oxide and 20-40 parts of titanium dioxide, and the briquette prepared by adopting the catalyst can only increase the strength of the briquette and reduce the pyrolysis temperature of the briquette.

When the sludge is oil sludge, the sludge briquette coal composition comprises the following components in parts by mass: 20-60 parts of oil sludge, 30-70 parts of coal powder, 1-10 parts of desulfurizer and 0-10 parts of catalyst, wherein oil-containing components in the oil sludge are used as adhesive.

When the sludge is municipal sludge, the sludge briquette coal composition comprises the following components in parts by mass: 20-60 parts of municipal sludge, 30-70 parts of coal powder, 1-10 parts of adhesive and 1-10 parts of desulfurizer.

When the sludge is waste activated clay, the sludge briquette coal composition comprises the following components in parts by mass: 20-60 parts of waste activated clay, 30-70 parts of coal powder, 1-10 parts of adhesive and 1-10 parts of desulfurizer.

When the sludge is slag discharge or dust removal fly ash of a power station boiler, the sludge briquette composition comprises the following components in parts by mass: 20-60 parts of slag discharging or dust removing fly ash of a power station boiler, 40-60 parts of coal powder, 1-10 parts of an adhesive and 1-10 parts of a desulfurizer.

Further, the content of each component can be adjusted adaptively according to actual production and required conditions.

The preparation method of the sludge briquette composition specifically comprises the following steps:

(1) the preparation method comprises the following steps of selecting 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 5-15 parts of cobalt chloride, 10-30 parts of calcium carbonate, 10-30 parts of pyroligneous acid and 1-10 parts of zinc oxide according to a calculated proportion, wherein the specific process for preparing the composite desulfurizer by using the formula comprises the following steps: dissolving potassium permanganate in water to prepare a potassium permanganate saturated solution, putting wood vinegar into a reaction kettle at normal temperature, adding the potassium permanganate saturated solution into the reaction kettle, heating the mixture to 50-60 ℃, and continuously stirring for 15-20 min to obtain a liquid component of the desulfurizer; grinding magnesium oxide, cobalt chloride and calcium carbonate into fine powder of 200 meshes, sequentially adding the ground powder into the liquid component, continuously stirring for 15-20 min, adding zinc oxide powder into the mixture, stirring to prepare slurry, drying the slurry desulfurizer mixture, and grinding into fine powder particles of 200 meshes for later use.

Compared with the desulfurizer obtained by directly mixing all components, the desulfurizer changes the mixing of solid and solid into the mixing of liquid and solid, so that all the components are mixed more uniformly, the solid components in the desulfurizer are wrapped inside potassium permanganate and pyroligneous acid in a particle form, and when molded coal is subjected to low-temperature dry distillation, the potassium permanganate and the pyroligneous acid on the surface of desulfurizer particles firstly act on pulverized coal, so that better desulfurization and denitration effects are achieved, and the obtained fuel is cleaner. Meanwhile, after potassium permanganate and pyroligneous acid on the surfaces of the particles react with the coal powder to generate gas, porous structures are formed on the surfaces of the particles, so that zinc oxide components in the particles can be conveniently and fully contacted with the coal powder and the catalyst, and the inhibition effect of other components on the catalyst is reduced.

adding sludge and an adhesive into the pulverized coal for mixing, stirring uniformly, adding desulfurizer powder and catalyst powder into the mixture, homogenizing and curing to uniformly mix and fully contact various materials, putting the mixture into a molding device for hot press molding, and finally air-drying.

The invention prepares the formed coal product by utilizing sludge produced by industry and municipal administration in a simple way, and in addition, the oily sludge is used in the process of preparing the formed coal, thereby effectively improving the combustibility of the formed coal fuel while realizing the harmless treatment of the sludge and the oily sludge.

Compared with the mode of treating sludge by using a pyrolysis process in the prior art, the method has the advantages that high temperature is not needed, the energy consumption is low, not only is the effective recycling of resources realized, but also waste materials are changed into valuable things, indexes such as the emission of flue gas and the emission of sulfur dioxide after burning of the finally obtained semi-coke can meet the environmental protection requirement, the environmental pollution is reduced, and the clean carbon product with high heat value can be obtained after the coal product is subjected to a low-temperature dry distillation process.

Example 1

The embodiment provides a method for preparing a briquette composition by using oil sludge, wherein the briquette composition comprises 20 parts of oil sludge, 70 parts of coal powder and 10 parts of a desulfurizer; wherein the oil sludge is selected from oil sludge generated in the processes of crude oil extraction, gathering and transportation, sewage treatment fields of oil refineries and the like, and the pulverized coal is crushed into particles with the particle size of 3 mm. Wherein a part of the oil sludge is used as a binder.

In this example, the desulfurizing agent was a sulfur-fixing type desulfurizing agent.

Adding oil sludge into the coal powder for mixing, stirring uniformly, adding desulfurizer powder into the mixture, homogenizing and curing to uniformly mix and fully contact various materials, putting the mixture into a molding device for hot press molding, and finally air-drying to obtain the environment-friendly coal.

Example 2

The embodiment provides a method for preparing a briquette composition by using oil sludge, wherein the briquette composition comprises 60 parts of oil sludge, 30 parts of coal powder and 10 parts of a desulfurizer; wherein the oil sludge is selected from oil sludge generated in the processes of crude oil extraction, gathering and transportation, sewage treatment fields of oil refineries and the like, and the pulverized coal is crushed into particles with the particle size of 3 mm. Wherein a part of the oil sludge is used as a binder.

Example 3

The embodiment provides a method for preparing a briquette composition by using municipal sludge, wherein the briquette composition comprises 20 parts of municipal sludge, 60 parts of coal powder, 10 parts of adhesive and 10 parts of desulfurizer; the municipal sludge is produced in the municipal sewage treatment industry, and the pulverized coal is crushed into particles with the particle size of 3 mm. Wherein the adhesive is oil asphalt or tar residue generated in the industrial production and the coal briquette pyrolysis process.

Adding municipal sludge and an adhesive into the coal powder for mixing, stirring uniformly, adding desulfurizer powder into the mixture, homogenizing and curing to uniformly mix and fully contact various materials, then putting the mixture into a molding device for hot press molding, and finally air-drying to obtain the environment-friendly coal.

Example 4

The embodiment provides a method for preparing a composition by using municipal sludge briquette, wherein the briquette composition comprises 60 parts of municipal sludge, 30 parts of coal powder, 5 parts of adhesive and 5 parts of desulfurizer; the municipal sludge is produced in the municipal sewage treatment industry, and the pulverized coal is crushed into particles with the particle size of 3 mm. Wherein the adhesive is oil asphalt or tar residue generated in the industrial production and the coal briquette pyrolysis process.

Example 5

The embodiment provides a method for preparing a briquette coal composition by using waste activated clay, wherein the briquette coal composition comprises 20 parts of waste activated clay, 60 parts of coal dust, 10 parts of a desulfurizer and 10 parts of an adhesive, the waste activated clay is waste activated clay generated in an oil refining process, and the coal dust is crushed into particles with the particle size of 3 mm. Wherein the adhesive is oil asphalt or tar residue generated in the industrial production and the coal briquette pyrolysis process.

Adding waste activated clay and an adhesive into the coal powder to mix, stirring uniformly, adding desulfurizer powder into the mixture, homogenizing and curing to uniformly mix and fully contact various materials, putting the mixture into a molding device for hot press molding, and finally air-drying to obtain the environment-friendly coal.

Example 6

The embodiment provides a method for preparing a briquette coal composition by using waste activated clay, wherein the briquette coal composition comprises 60 parts of waste activated clay, 30 parts of coal dust, 5 parts of a desulfurizer and 5 parts of an adhesive, the waste activated clay is waste clay generated in an oil refining process, and the coal dust is crushed into particles with the particle size of 3 mm. Wherein the adhesive is oil asphalt or tar residue generated in industrial production and in the coal briquette pyrolysis process.

Example 7

The embodiment provides a method for preparing a briquette composition by using slag discharging or dust removing fly ash of a power station boiler, wherein the briquette composition comprises 20 parts of slag discharging or dust removing fly ash of the power station boiler, 60 parts of coal powder, 10 parts of an adhesive and 10 parts of a desulfurizer; firstly, the slag or dust removal fly ash and coal powder of the power station boiler are crushed into the granularity meeting the requirement, and the preferred granularity is 3 mm. The adhesive is oil asphalt or tar residue produced in the industrial production and coal briquette pyrolysis process.

Adding the electric station boiler slag or dust removal fly ash and the adhesive into the pulverized coal for mixing, stirring uniformly, adding the desulfurizer powder into the mixture, homogenizing and curing to uniformly mix and fully contact various materials, putting the mixture into a molding device for hot press molding, and finally air-drying to obtain the environment-friendly coal.

Example 8

The embodiment provides a method for preparing a briquette composition by using slag discharging or dust removing fly ash of a power station boiler, wherein the briquette composition comprises 60 parts of slag discharging or dust removing fly ash of the power station boiler, 20 parts of coal powder, 5 parts of an adhesive and 5 parts of a desulfurizer; firstly, the slag or dust removal fly ash and coal powder of the power station boiler are crushed into the granularity meeting the requirement, and the preferred granularity is 3 mm. The adhesive is oil asphalt or tar residue produced in the industrial production and coal briquette pyrolysis process.

Example 9

In this embodiment, the desulfurizing agent is a compound i desulfurizing agent, wherein the compound i desulfurizing agent comprises the following components: 15 parts of magnesium oxide, 30 parts of potassium permanganate, 22.5 parts of calcium carbonate, 7.5 parts of cobalt chloride and 25 parts of wood vinegar, and the compound I desulfurizing agent is prepared into powder according to the formula of the embodiment.

Adding oil sludge into the coal powder for mixing, stirring uniformly, adding the composite type I desulfurizer powder into the mixture, homogenizing and curing to uniformly mix and fully contact various materials, and then putting the mixture into a molding device for hot press molding to obtain the environment-friendly coal.

Example 10

In this embodiment, the desulfurizing agent is a compound type ii desulfurizing agent, wherein the compound type ii desulfurizing agent comprises the following components: 15 parts of magnesium oxide, 30 parts of potassium permanganate, 20 parts of calcium carbonate, 5 parts of cobalt chloride, 25 parts of pyroligneous acid and 5 parts of zinc oxide, and according to the formula of the embodiment, the compound II desulfurizer is prepared into fine powder with the granularity of 200 meshes through a reaction kettle processing technology.

Example 11

The embodiment provides a method for preparing a briquette composition by using oil sludge, wherein the briquette composition comprises 60 parts of oil sludge, 30 parts of coal powder, 10 parts of a desulfurizer and 0.5 part of a catalyst; wherein the oil sludge is selected from oil sludge generated in the processes of crude oil extraction, gathering and transportation, sewage treatment fields of oil refineries and the like, and the coal powder is crushed into particles with the particle size of 3 mm. Wherein a part of the oil sludge is used as a binder.

In this embodiment, the desulfurizing agent is a compound i desulfurizing agent, wherein the compound i desulfurizing agent comprises the following components: 15 parts of magnesium oxide, 30 parts of potassium permanganate, 22.5 parts of calcium carbonate, 7.5 parts of cobalt chloride and 25 parts of pyroligneous acid, and according to the formula of the embodiment, the compound II desulfurizer is prepared into fine powder with the granularity of 200 meshes by a reaction kettle processing technology.

In this example, a catalyst was added, wherein the catalyst comprised the following components: laterite-nickel ore 40, calcium oxide 30 and titanium dioxide 30.

Adding oil sludge into the pulverized coal for mixing, stirring uniformly, adding composite type I desulfurizer powder and catalyst powder into the mixture, homogenizing and curing to uniformly mix various materials, fully contacting, and putting the mixture into a molding device for hot press molding to obtain the environment-friendly coal.

Example 12

In this example, a catalyst was added, wherein the catalyst comprised the following components: 40 parts of laterite nickel ore, 30 parts of calcium oxide and 30 parts of titanium dioxide.

Adding oil sludge into the pulverized coal for mixing, stirring uniformly, adding composite II desulfurizer powder and catalyst powder into the mixture, homogenizing and curing to uniformly mix various materials, fully contacting, and putting the mixture into a molding device for hot press molding to obtain the environment-friendly coal.

Example 13

In this embodiment, the desulfurizing agent is a compound type ii desulfurizing agent, wherein the compound type ii desulfurizing agent comprises the following components: 15 parts of magnesium oxide, 30 parts of potassium permanganate, 20 parts of calcium carbonate, 5 parts of cobalt chloride, 25 parts of pyroligneous acid and 5 parts of zinc oxide, and grinding the components into fine powder, wherein the desulfurizer is directly added into a formula of the briquette coal composition without a reaction kettle processing technology before being added into coal powder and oil sludge.

Adding oil sludge into the coal powder for mixing, stirring uniformly, adding magnesium oxide, potassium permanganate, calcium carbonate, cobalt chloride, pyroligneous acid, zinc oxide powder and catalyst powder into the mixture, then uniformly mixing and curing the mixture to ensure that various materials are uniformly mixed and fully contacted with each other, and then putting the mixture into a molding device for hot-press molding to obtain the environment-friendly molded coal.

Comparative example

In this example, the desulfurizing agent described in the prior art publication No. CN101560426A was used as the desulfurizing agent.

Test examples

Drying the molded coal obtained in the above embodiments, then preparing a high-calorific-value clean type carbon product through a low-temperature dry distillation process, and measuring parameters of the molded coal in the above embodiments, including strength, water resistance and combustion value of the molded coal.

The strength of the briquette is determined by the method of determining the falling strength of the industrial briquette according to MT/T925-2004, the briquette samples produced in the examples are freely dropped onto a steel plate with specified thickness from a height of 2m, briquette blocks with the granularity of more than 13mm in the dropped briquette are dropped again for 3 times, and the falling strength of the briquette is represented by the mass percentage of the briquette blocks with the granularity of more than 13mm after the 3 rd dropping in the mass of the prototype coal sample.

The water resistance test method of the briquette comprises the following steps: the briquette samples produced in the embodiments are soaked in water at room temperature for two hours, and then freely fall onto a steel plate with specified thickness from a height of 2m, briquette blocks with the granularity of more than 13mm in the falling briquette are fallen again for 3 times, and the falling strength of the briquette is represented by the mass percentage of the briquette blocks with the granularity of more than 13mm after the 3 rd fall to the mass of the prototype coal sample before soaking.

The combustion value of the briquette is tested according to GB213-87, and the test results are shown in the following table.

In order to further verify that the product obtained by the invention is clean briquette, the test example also determines the oil recovery rate and the content of harmful gas after combustion of the briquette obtained by the above example after low-temperature dry distillation, and compares the oil recovery rate and the content of harmful gas with the briquette product prepared by using raw coal. The specific results are shown in table 1 below:

TABLE 1

As can be seen from the comparison of the data in the example in Table 1, the higher the contents of the asphalt and the tar residue in the oil sludge are as the binder for the briquette, the higher the strength of the briquette is. The higher the content of the desulfurizer in the briquette combined formula is, the lower the sulfur dioxide emission amount after burning of the obtained semi coke is.

The sulfur dioxide emission amount in tail gas obtained by using the compound type I desulfurizer in the briquette composition is lower than that of a sulfur-fixing desulfurizer, and the briquette composition is more environment-friendly. By adding zinc oxide into the desulfurizer, the emission of sulfur dioxide in tail gas can be further improved, so that the emission of sulfur dioxide after low-temperature dry distillation and combustion of the briquette is lower.

Weight loss rate test

Selecting a quantitative briquette sample, heating from 25 ℃ to 900 ℃ at the heating rates of 10 ℃/min, 20 ℃/min and 30 ℃/min respectively under the atmosphere of high-purity nitrogen of 60mL/min, measuring the weight loss rate of the briquette at each temperature node, and drawing a thermogravimetric curve, wherein the larger the weight loss rate is, the higher the pyrolysis rate of the briquette at the temperature is.

TABLE 2

As can be seen from the comparison of the data of the example 9 and the comparative example in the table 2, after the wood vinegar is added into the desulfurizer, not only can the strength of the molded coal be increased, but also the wood vinegar has a good denitration effect, and the emission of nitrogen oxides in tail gas is effectively reduced.

The comparison of the data of the embodiment 9 and the embodiment 10 shows that the addition of zinc oxide in the desulfurizing agent has better desulfurizing effect, so that the emission of sulfur dioxide in tail gas is reduced from 0.18 to 0.09, namely, the semi-coke product obtained by adding zinc oxide in the desulfurizing agent is cleaner.

It can be seen from the comparison of the data in examples 9 and 11 that the catalyst is added to the formulation of the sludge briquette composition, which not only increases the strength of the briquette, but also enables the briquette to achieve a higher pyrolysis rate at a lower pyrolysis temperature, i.e., the catalyst can effectively reduce the pyrolysis temperature of the briquette, but the reduction of the pyrolysis temperature of the briquette is limited because the metal sulfide is generated by the reaction of the metal salt in the desulfurizing agent and the sulfur in the formulation of the briquette composition during the pyrolysis process, and the metal sulfide has a poisoning effect on the catalyst and affects the catalytic activity of the catalyst.

As can be seen from the comparison of the data in example 11 and example 12, the zinc oxide in the desulfurizing agent has an accelerating effect on the catalyst, and can reduce the pyrolysis temperature of the briquette to a greater extent, mainly because the zinc oxide has a protective effect on the catalyst and prevents the catalyst from being deactivated.

It can be known from the comparison of the data in the embodiment 12 and the embodiment 13 that the composite desulfurizer is heated, mixed and stirred in the reaction kettle before being added into the formula of the molded coal composition, so that the components in the desulfurizer are mixed more fully, the desulfurization and denitration effects are better, the uniformly mixed desulfurizer can be in full contact with the catalyst, and the inhibition effect on the catalyst is obviously reduced.

In addition, the calorific value of the semi-coke obtained finally by adopting the briquette composition formula after combustion is close to the calorific value of the briquette fuel prepared from raw coal, compared with the mode of treating sludge by using a pyrolysis process in the prior art, the briquette composition prepared by using sludge can effectively utilize resources in the sludge while simplifying the sludge treatment process, change waste into valuable, obtain the clean fuel with high calorific value, and has good popularization and application values.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. The sludge briquette composition is characterized by comprising sludge, coal dust, a desulfurizer, a binder and a catalyst, wherein the binder is selected from at least one of oil asphalt and tar residue.

2. The sludge briquette composition according to claim 1, wherein the sludge comprises at least one of oil sludge, municipal sludge, and spent activated clay.

3. The sludge briquette composition according to claim 2, wherein the oil sludge is selected from the group consisting of oil sludge produced during crude oil extraction, oil sludge produced during oil field gathering and transportation, oil sludge produced at sewage treatment sites of oil refineries, contaminated soil caused by oil used in steel smelting industry, oil sludge produced during offshore oil field extraction, coastlines and river margins contaminated by heavy oil hydrocarbons used in shipbuilding and ship repair, water bodies caused by oil leakage due to accidents of oil tanker ships, and surface oil sludge.

4. The sludge briquette composition according to claim 2, which is characterized by comprising the following components in parts by mass: 20-60 parts of sludge, 30-70 parts of coal powder, 0.5-10 parts of desulfurizer, 0-10 parts of adhesive and 0-10 parts of catalyst.

5. The sludge briquette composition according to claim 4, which is characterized by comprising the following components in parts by mass: 20-60 parts of oil sludge, 30-70 parts of coal powder, 1-10 parts of desulfurizer and 0-10 parts of catalyst, wherein oil-containing components in the oil sludge are used as adhesive.

6. The sludge briquette composition according to claim 4, which is characterized by comprising the following components in parts by mass: 20-60 parts of municipal sludge, 30-70 parts of pulverized coal, 1-10 parts of an adhesive, 1-10 parts of a desulfurizer and 0-10 parts of a catalyst.

7. The sludge briquette composition according to claim 4, which is characterized by comprising the following components in parts by mass: 20-60 parts of waste activated clay, 30-70 parts of coal powder, 1-10 parts of adhesive, 1-10 parts of desulfurizer and 0-10 parts of catalyst.

8. The sludge briquette composition according to claim 4, which is characterized by comprising the following components in parts by mass: 20-60 parts of slag discharging or dust removing fly ash of a power station boiler, 40-60 parts of coal powder, 1-10 parts of an adhesive, 1-10 parts of a desulfurizer and 0-10 parts of a catalyst.

9. The sludge briquette composition according to any one of claims 4 to 8, wherein the desulfurizing agent is divided into a sulfur-fixing type desulfurizing agent and a composite desulfurizing agent, and the composite desulfurizing agent can also be selected from composite desulfurizing agents prepared by a synthesis process, and comprises the following chemical components: 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 5-15 parts of cobalt chloride, 10-30 parts of calcium carbonate, 10-30 parts of wood vinegar and 1-10 parts of zinc oxide.

10. The preparation method of the sludge briquette composition is characterized by comprising the following steps:

(1) selecting 10-30 parts of magnesium oxide, 20-40 parts of potassium permanganate, 5-15 parts of cobalt chloride, 10-30 parts of calcium carbonate and 10-30 parts of wood vinegar according to a calculated ratio to prepare desulfurizer powder;

then adding desulfurizer powder and catalyst powder into the mixture,