CN106147912A - A kind of moulded coal preparation method of the low-order coal of solid sulfur high thermal stability - Google Patents
A kind of moulded coal preparation method of the low-order coal of solid sulfur high thermal stability Download PDFInfo
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Abstract
The invention provides a kind of low order moulded coal preparation method that sulfur effectively can be removed and have high thermal stability, wherein make use of can the effective sodium humate binding agent of the cold strength of maintenance product of coal and can be effectively improved the inorganic binder of calorific intensity, so that fine coal is maintained preferable framing structure during being shaped to moulded coal, thus type burning of coal is the most abundant or is more suitable for pyrolysis.Additionally, due to the sulfur fixation of the calcium component in briquette prod, the present invention can be greatly enhanced the utilization rate of fine coal so that it is becomes the clean energy resource of high-quality and environmental protection, and the present invention the most also has the beneficial effect that technique is simple, with low cost.
Description
Technical field
The present invention relates to a kind of low order moulded coal preparation method, particularly one have captured sulfur result and
The moulded coal preparation method that calorific intensity is good.It can be widely applied to the briquette molding technique of fine coal, especially
Prepared by the moulded coal being applicable to low order fine coal.
Background technology
The resources supplIes of China presents the situation of " oil starvation, few gas, coal resources relative abundance " always,
Coal is as the main energy sources of China, and it accounts for about about 70% in disposable energy resource structure, it is contemplated that arrive
The consumption of coal of China in 2015 will account for about 65%.Therefore within the quite a long time,
Ensureing of power self-support rate will continue the large-scale use from coal resources, the energy war based on coal
Lve Shi China process of industrialization inevitable stage.
Owing to the formation of coal is acted on by many factors, different according to its structure and composition, coal divides
For brown coal, bituminous coal and the big class of anthracite 3, and every big class is divided into some groups, and its metabituminous coal can divide
For lower-grade metamorphic bituminous and mesometamorphism bituminous coal, lower-grade metamorphic bituminous also it is ub-bituminous coal, is referred to as together with brown coal
" low-order coal ".Generally, coal buried depth increases, and its degree of coalification increases, carbon content also phase
Should increase, its coal rank are the highest.Low-order coal accounts for the most at high proportion in coal in China reserves and yield.In
The Third National coal field prediction of coal geological exploration general bureau of state, China's low-order coal reserves account for the whole nation and have verified coal
More than the 55% of reserves, reaches 561,200,000,000 tons, and wherein brown coal account for 12.7%, and low-disintegration coal accounts for 42.5%.
Current energy resource structure and exploitation of coal resources present situation facilitate low-order coal in China's energy resource supply
Critical role, the importance that low-order coal effectively utilizes rises the most increasingly, and in view of environmental protection aspect increasingly
Perfect laws and regulations, carry out high-efficiency cleaning utilization to it and are just obtaining government, research unit and enterprise
Extensively pay attention to.
But, China fails to realize the high level of resource in the coal utilization mode of direct burning at present
Change and utilize, discharge substantial amounts of pollutant simultaneously.Comparing with this, pyrolysis upgrading technology is due to its condition temperature
With and remarkable benefit, one of maximally effective low-order coal Land use systems being well recognized as.Due to low-order coal
In chemical constitution, side chain is more, and hydrogen, oxygen content are higher, cause its volatile matter content height high, aqueous,
Oxygen-containing spontaneous combustion many, easy, calorific value are low.Therefore according to the feature that low-order coal volatile matter and hydrogen content are high, logical
The staged conversion crossing pyrolytic technique utilizes, and can first obtain the oil of high added value, gas and chemicals, then will
Residue semicoke carries out burning or gasifying, it is achieved thereby that the cascade utilization of coal resources.Pyrolysis upgrading skill
On the one hand art improves the efficiency of coal utilization, on the other hand makes the low-order coal such as the brown coal being difficult by obtain
Arrive effective utilization, also can greatly reduce the pollution of environment simultaneously.
Further, since the direct burning of coal can produce substantial amounts of sulfur nitrogen oxides, therefore at coal
In clean energyization application, need to add wherein sulphur-fixing agent, so in burning and the dry distilling of coal
Journey just can generate solid-state sulfate with the reaction of Salmon-Saxl in coal, thus prevent sulfiding gas to be discharged into air
In, alleviate the material to atmospheric pollution.Additionally, either carry out burning or being pyrolyzed, most
Kiln or reactor are all adapted only to use block coal, are pyrolyzed work at such as LLC technique and DG etc.
In skill, being also mainly pyrolyzed lump coal, substantial amounts of fine coal is then difficult to be had by pyrolysis upgrading
Effect utilizes, it is therefore desirable to utilizes binding agent by coal powder formation, is fabricated to have figurate moulded coal.
It is desirable that the moulded coal (coal briquette) after molding should have the highest hot and cold mechanical strength and thermally-stabilised
Property, the highest protection against the tide, water resistance and water logging intensity, in putting into stove, fuel value is high, and burning after heat is strong
Degree height, whereabouts percentage of damage is low, without ash, pollution-free and simple to operate.
For some demand in above-mentioned coal utilization, the i.e. desulfurization of the molding of fine coal, bonding and coal
And the cold and hot mechanical strength of moulded coal and thermal stability requirement, have been carried out substantial amounts of R&D work also
Existing considerable patented technology, such as, in Chinese patent CN 101444695A, disclose one
Energy-saving and sulfur-fixing agent.This technique is by potassium permanganate, iron sesquioxide, potassium nitrate, potassium hydroxide, oxidation
The chemical raw materials such as calcium are mixed and made into sulphur-fixing agent by different proportion.This sulphur-fixing agent is added when coal burning,
Can effectively remove the sulfide that coal burning produces.But, owing to being to add this when lump coal burns
Plant sulphur-fixing agent, therefore there is the sulfide and sulphur-fixing agent effective contact rate that can not fully mix and produce
Relatively low shortcoming, thus it is unable to reach preferable removal effect.Further for depositing with fine coal form in a large number
Low-order coal, can not directly apply.
Additionally, Chinese patent CN 102061208A discloses a kind of brown coal briquette preparation technology.Specifically
Ground, mixes, at 120 DEG C brown coal, oil-sand, Masson Pine are divided by this technique, additive etc. by a certain percentage
Hot pressing obtains moulded coal.But, the shortcoming of this technology is complicated process of preparation, and the consumption of binding agent is high,
Element sulphur in coal can not effectively be removed simultaneously.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides one effectively can remove sulfur
And there is the low order moulded coal preparation method of high thermal stability, can effectively keep moulded coal to produce owing to make use of
The sodium humate binding agent of the cold strength of product and the inorganic binder that calorific intensity can be effectively improved, thus
Fine coal is made to be maintained preferable framing structure during being shaped to moulded coal, so that moulded coal
Burning the most abundant or be more suitable for pyrolysis.Additionally, the calcium component in briquette prod can also rise
To sulfur fixation, therefore the present invention can be greatly enhanced the utilization rate of fine coal so that it is becomes high-quality and ring
The clean energy resource protected, the present invention the most also has the beneficial effect that technique is simple, with low cost.
According to an aspect of the invention, it is provided a kind of moulded coal preparation method, it is characterised in that
Fine coal adds inorganic binder and the Lignitic Humic Acid of 5%-8% (weight) of 2%-5% (weight)
Sodium binding agent is sufficiently mixed, and is shaped mixed material processing and generating briquette prod.
Further according to the moulded coal preparation method that the present invention is above-mentioned, wherein Lignitic Humic Acid sodium binding agent is adopted
Prepare by following technique:
Heating the water of 100%-180% (weight) in reative cell, water is heated to 80 DEG C-95 DEG C
Time add sodium hydroxide and the calcium system thing of 1%-5% (weight) of 3%-8% (weight), dissolve completely
The Lignitic Humic Acid of rear addition 100% (weight), continues stirring and carries out being warming up to 90 DEG C-100 DEG C
Reaction temperature is reacted, and the response time is 30-50min, thus generates Lignitic Humic Acid sodium binding agent.
The moulded coal preparation method provided according to invention, is further characterized in that, described inorganic binder is
One or more from following middle selection: bentonite, Kaolin, cement, waterglass, carbide slurry,
Phosphate, sulfate.
According to above-mentioned moulded coal preparation method, it is characterised in that described inorganic binder with addition of amount excellent
Selection of land is 3% (weight).
According to above-mentioned moulded coal preparation method, it is characterised in that described Lignitic Humic Acid sodium binding agent
It is preferably 6% (weight) with addition of amount.
According to moulded coal preparation method provided by the present invention, it is further characterized in that, described adds in fine coal
Enter inorganic binder and Lignitic Humic Acid sodium binding agent carry out well-mixed temperature be maintained at 60 DEG C with
On.
According to above-mentioned moulded coal preparation method, calcium system therein thing is or many from following middle selection
: quick lime, Calx.
According to above-mentioned moulded coal preparation method, wherein the joining of water in the preparation of Lignitic Humic Acid sodium binding agent
Dosage is preferably 140% (weight).
According to above-mentioned moulded coal preparation method, wherein hydroxide in the preparation of Lignitic Humic Acid sodium binding agent
Sodium with addition of amount be preferably 5% (weight).
According to above-mentioned moulded coal preparation method, wherein calcium system thing in the preparation of Lignitic Humic Acid sodium binding agent
With addition of amount be preferably 3% (weight).
According to above-mentioned moulded coal preparation method, wherein reaction temperature in the preparation of Lignitic Humic Acid sodium binding agent
Degree is preferably 100 DEG C, and the response time is preferably 45min.
According to above-mentioned moulded coal preparation method, can use roller ball press or screw extrusion machine for producing coal bars
Fine coal is shaped thus obtains briquette prod.
The beneficial effects of the present invention is, owing to employing sodium humate binding agent and inorganic binder shape
The compound binding agent become, wherein inorganic binder part uses bentonite or chemical composition similar to it
Material, such as bentonite, Kaolin, cement, waterglass, carbide slurry, phosphate, sulfate,
It has good hydrophilic property, cohesion is strong, source is wide and the feature such as low cost, and prepared moulded coal is resistance to
High temperature, Heat stability is good.Sodium humate binding agent then contains substantial amounts of free humic acid, free
Humic acids is a kind of colloid, has highly polar, and therefore in forming process, External Force Acting makes coal grain
Between be in close contact, now there is the molecular separating force that highly polar humic acids molecule makes coal intergranular combine and obtain
The molding with reinforcement, maintains the cold strength of briquette prod the most effectively, and framing structure is preferable.This
Outer humic acid binding agent can bond brown coal in pyrolytic process effectively so that moulded coal keeps higher strong
Degree, and can prevent the broken dust produced of brown coal pyrolysis from entering in pyrolysis gas.
Additionally, Normal practice is to use calcium based sulphur-fixation reagent to carry out desulfurization in prior art, its principle is
The SO generated during calcium component in coal and coal burning2And SO3Chemically reactive, is formed solid
State residue thus stay in coal ash, therefore can play the effect of solid sulfur.Many employings in prior art
Calcium based sulphur-fixation reagent has traditional limestone, quick lime, Calx, wollastonite and novel artificial calcio
Sulphur-fixing agent, shell sulphur-fixing agent and nanometer CaCO3Sulphur-fixing agent etc., but these single calcium system chemical combination
Thing easily produces Sintering Problem or resolution problem when high temperature, therefore causes activity to reduce thus solid sulfur
Rate is low.In contrast, the sodium humate binding agent of present invention employing and being combined of inorganic binder formation
Binding agent then has more advantage.Owing to the existence of organic binder bond can make the microcosmic of calcium based compound tie
Structure is improved, and such as pore structure, specific surface area, pore size, pore size distribution and specific pore volume are long-pending
Microstructure, therefore improves the activity of calcium based compound, and then improves its sulfur-fixing rate.
Accompanying drawing explanation
Technical scheme is entered one by the following drawings and the embodiment being described with reference to the accompanying
The description of step, it should be appreciated that parameter area disclosed in this invention and technological process are only used for showing
Example ground explanation best mode for carrying out the invention, it is understood not to for the scope of the present invention
Form any restriction.For equivalent or the phase jljl of the material described in the disclosure and have
Identical approximation technique effect with addition of amount should be considered to fall into present invention technology required for protection model
Enclose.
Accompanying drawing 1 is the flow chart of an embodiment of the briquette preparation technology according to the present invention；
Accompanying drawing 2 show the moulded coal prepared by an embodiment of the briquette preparation technology according to the present invention
Solid sulfur index chart after burning.
Detailed description of the invention
The embodiment of the present invention is merely cited for the present invention, and limits the present invention never in any form.This
Outward, owing to the present invention is based on the improvement made for the moulding process of moulded coal in prior art, therefore,
In the preparation technology of moulded coal, having some steps is routine techniques step and not necessarily sport technique segment,
The such as screening shown in Fig. 1, pulverize, pinch stir, puddling etc., but for keeping method step
Integrity and clear for the sake of, these steps shown in Figure 1, it is noted that its
It is not construed as essential features and constitutes limiting the scope of the invention.
Embodiment one
Heating the water of 140% (weight) in reative cell, water is heated to when 90 DEG C adding 5%
The sodium hydroxide of (weight) and the calcium hydroxide of 3% (weight), add 100% (weight after dissolving completely
Amount) Lignitic Humic Acid, continue stirring and carry out being warming up to the reaction temperature of 100 DEG C and react, instead
It is 45min between Ying Shi, generates Lignitic Humic Acid sodium binding agent, fine coal is straight to ball block through crusher in crushing
Footpath below 2mm, the bentonite adding 3% (weight) left and right in the fine coal after crushing fully mixes
Closing, mixing is rear adds the Lignitic Humic Acid being maintained at 6% (weight) left and right at a temperature of 65 DEG C
Sodium binding agent carries out rerolling, and mixed material is through obtaining briquette prod to roller ball press molding.
The moulded coal prepared according to said method is carried out briquette strength test, and result is: moulded coal cold strength
Reach 472N/, 2m fall strength of briquette more than 80%, heat stability more than 85%.
Briquette prod being put into fixed-bed pyrolysis stove be pyrolyzed, being pyrolyzed the fastest rate of heat addition is 25 DEG C
min-1, pyrolysis final temperature at 580 DEG C, at this temperature insulation one hour after come out of the stove, obtain tar, gas,
Semicoke product, then carries out strength test to the moulded coal after pyrolysis, and result is: after pyrolysis, intensity is 365N/
Individual, 2m fall strength of briquette more than 80%.
Embodiment two
Heating the water of 140% (weight) in reative cell, water is heated to when 90 DEG C adding 6%
The sodium hydroxide of (weight) and the calcium oxide of 3% (weight), add 100% (weight after dissolving completely
Amount) Lignitic Humic Acid, continue stirring and carry out being warming up to the reaction temperature of 100 DEG C and react, instead
It is 50min between Ying Shi, generates Lignitic Humic Acid sodium binding agent, fine coal is straight to ball block through crusher in crushing
Footpath below 2mm, the Kaolin adding 3% (weight) left and right in the fine coal after crushing fully mixes
Closing, mixing is rear adds the Lignitic Humic Acid being maintained at 6% (weight) left and right at a temperature of 70 DEG C
Sodium binding agent carries out rerolling, and mixed material is through obtaining briquette prod to roller ball press molding.
The moulded coal prepared according to said method is carried out briquette strength test, and result is: moulded coal cold strength
Reach 490N/, 2m fall strength of briquette more than 80%, heat stability more than 85%.
Briquette prod is put into fixed-bed pyrolysis stove be pyrolyzed, in pyrolysis parameters of rock such as embodiment one
Sample, being i.e. pyrolyzed the fastest rate of heat addition is 25 DEG C of min-1, pyrolysis final temperature, at 580 DEG C, is protected at this temperature
Temperature was come out of the stove after one hour, obtains tar, gas, semicoke product, then carries out the moulded coal after pyrolysis by force
Degree test, result is: after pyrolysis, intensity is 372N/, 2m fall strength of briquette more than 80%.
Embodiment three:
Heating the water of 140% (weight) in reative cell, water is heated to when 90 DEG C adding 6%
The sodium hydroxide of (weight) and the calcium hydroxide of 2% (weight), add 100% (weight after dissolving completely
Amount) Lignitic Humic Acid, continue stirring and carry out being warming up to the reaction temperature of 100 DEG C and react, instead
It is 50min between Ying Shi, generates Lignitic Humic Acid sodium binding agent, fine coal is straight to ball block through crusher in crushing
Footpath below 2mm, the bentonite adding 3% (weight) left and right in the fine coal after crushing fully mixes
Closing, mixing is rear adds the Lignitic Humic Acid being maintained at 6% (weight) left and right at a temperature of 65 DEG C
Sodium binding agent carries out rerolling, and mixed material is through obtaining briquette prod to roller ball press molding.
The moulded coal prepared according to said method is carried out briquette strength test, and result is: moulded coal cold strength
Reach 511N/, 2m fall strength of briquette more than 85%, heat stability more than 85%.
Briquette prod being put into fixed-bed pyrolysis stove be pyrolyzed, being pyrolyzed the fastest rate of heat addition is 25 DEG C
min-1, pyrolysis final temperature at 580 DEG C, at this temperature insulation one hour after come out of the stove, obtain tar, gas,
Semicoke product, then carries out strength test to the moulded coal after pyrolysis, and result is: after pyrolysis, intensity is 407N/
Individual, 2m fall strength of briquette more than 85%.
After the moulded coal being prepared from according to above-mentioned three kinds of embodiments is calcined, coal ash is carried out microcosmic sight
Survey, find to present between the granule of coal ash grain that the column hole that interconnects, granule be clear, hole
Smoothness, almost without dead hole and isolated hole, therefore illustrates that this grain structure of use of compound binding agent subtracts
Lack internal flow and the diffusional resistance of gas, beneficially the carrying out on vulcanization reaction surface therein,
The most this structure can reach more preferably captured sulfur result.
From the experimental data chart shown in Fig. 2, it can be seen that according to the moulded coal preparation method system of the present invention
For the moulded coal gone out, there is splendid captured sulfur result.Fig. 2 show the right of desulfurization efficiency after one group of coal combustion
According to table, the coal sulfur content selected by the experiment of this group is 1.01%, and experiment is divided into three groups, and first group is fine coal
Directly burning, is not added with any calcium series sulfur-fixation agent；Second group is that fine coal is straight with a certain proportion of calcium oxide
Connect doping to burn；3rd group is that fine coal bonds with through Lignitic Humic Acid sodium disclosed in this invention
Agent carries out mixing and burning after molding, wherein uses identical with the calcium oxide that second group is directly adulterated
The calcium oxide of percentage by weight carries out the preparation of Lignitic Humic Acid sodium binding agent, and compound by prepare
Binding agent carries out mixing with fine coal and drying and moulding.Fig. 2 data show, when fine coal directly burns,
The desulfurization efficiency of himself ash is 21%；When the calcium oxide of fine coal and 2% ratio (weight) directly mixes
Closing after-combustion, its desulfurization efficiency is 41%；Fine coal and employing compound binding agent system disclosed in this invention
After compound binding agent prepared by Preparation Method, calcium oxide by 2% (weight) carries out mixing molding, its
Combustion desulfurization efficiency is 65%, when fine coal with use compound binding agent preparation method disclosed in this invention,
After the compound binding agent prepared with the calcium oxide of 3% (weight) carries out mixing molding, its combustion desulfurization
Efficiency is 82%.It can be seen that the method disclosed in the present desulfurization efficiency is higher.This is due to oxygen
Change calcium to have added in preparation adhesive process, then when binding agent mixes with coal dust, calcium
Element is able to be fully contacted with coal dust, and the most fixed-type with fine coal, had the most both added and has connect
The long-pending compactness that adds again of contacting surface, therefore has compared to for directly adding calcium constituent in pulverized coal friring
There is higher desulfurization efficiency.
Although describing the present invention by reference to exemplary embodiment, but it is to be understood that the present invention
It is not limited in disclosed exemplary embodiment.And the scope of attached claims also should be by
Give broadest explanation, in order to contain and meet the equivalent modifications of spirit of the present invention, deformation, Yi Jiyu
The proportioning of this equivalence and material.
Claims (10)
1. a moulded coal preparation method, it is characterised in that add 2%-5%'s (weight) in fine coal
The Lignitic Humic Acid sodium binding agent of inorganic binder and 5%-8% (weight) is sufficiently mixed, to mixed
Material after conjunction is shaped processing and generating briquette prod.
Moulded coal preparation method the most according to claim 1, it is characterised in that described brown coal humic
Acid sodium binding agent uses following technique to prepare:
Heating the water of 100%-180% (weight) in reative cell, water is heated to 80 DEG C-95 DEG C
Time add sodium hydroxide and the calcium system thing of 1%-5% (weight) of 3%-8% (weight), dissolve completely
The Lignitic Humic Acid of rear addition 100% (weight), continues stirring and carries out being warming up to 90 DEG C-100 DEG C
Reaction temperature is reacted, and the response time is 30-50min, thus generates Lignitic Humic Acid sodium binding agent.
Moulded coal preparation method the most according to claim 2, is further characterized in that, described inorganic viscous
Knot agent is one or more from following middle selection: bentonite, Kaolin, cement, waterglass, electricity
Stone mud, phosphate, sulfate.
Moulded coal preparation method the most according to claim 3, it is characterised in that described inorganic binder
Be 3% (weight) with addition of amount.
Moulded coal preparation method the most according to claim 3, it is characterised in that described brown coal humic
Acid sodium binding agent is 6% (weight) with addition of amount.
Moulded coal preparation method the most according to claim 3, it is characterised in that described in fine coal
Add inorganic binder and Lignitic Humic Acid sodium binding agent carry out well-mixed temperature be maintained at 60 DEG C with
On.
Moulded coal preparation method the most according to claim 3, wherein said calcium system thing is from following
Middle selection one or more: quick lime, Calx.
Moulded coal preparation method the most according to claim 3, wherein Lignitic Humic Acid sodium binding agent
In preparation, water is 140% (weight) with addition of amount.
Moulded coal preparation method the most according to claim 3, wherein Lignitic Humic Acid sodium binding agent
In preparation, sodium hydroxide is 5% (weight) with addition of amount.
Moulded coal preparation method the most according to claim 3, is wherein preparing Lignitic Humic Acid sodium
During binding agent, calcium system thing is 3% with addition of amount, and the preparation reaction temperature of Lignitic Humic Acid sodium binding agent is
100 DEG C, the response time is 45min.
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| CN110540850A (en) * | 2019-10-17 | 2019-12-06 | 贵州富燃环保科技有限公司 | Lignite upgrading method and structure thereof |
| CN110671703A (en) * | 2019-10-17 | 2020-01-10 | 贵州富燃环保科技有限公司 | Method and structure for preparing clean carbon-coupled garbage clean incineration by coal dry distillation |
| CN112577298A (en) * | 2021-02-03 | 2021-03-30 | 刘冠诚 | Lignite high-frequency drying device and forming process |
| CN112646627A (en) * | 2020-12-21 | 2021-04-13 | 天津渤化永利化工股份有限公司 | Granular briquette and preparation method thereof |
| CN113214880A (en) * | 2021-05-28 | 2021-08-06 | 陕西榆能集团能源化工研究院有限公司 | Coal ash-based high-sulfur-fixation coal binder and preparation method and application thereof |
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| CN110540850A (en) * | 2019-10-17 | 2019-12-06 | 贵州富燃环保科技有限公司 | Lignite upgrading method and structure thereof |
| CN110671703A (en) * | 2019-10-17 | 2020-01-10 | 贵州富燃环保科技有限公司 | Method and structure for preparing clean carbon-coupled garbage clean incineration by coal dry distillation |
| CN110540850B (en) * | 2019-10-17 | 2022-08-12 | 贵州富燃环保科技有限公司 | Lignite upgrading method and structure thereof |
| CN112646627A (en) * | 2020-12-21 | 2021-04-13 | 天津渤化永利化工股份有限公司 | Granular briquette and preparation method thereof |
| CN112577298A (en) * | 2021-02-03 | 2021-03-30 | 刘冠诚 | Lignite high-frequency drying device and forming process |
| CN113214880A (en) * | 2021-05-28 | 2021-08-06 | 陕西榆能集团能源化工研究院有限公司 | Coal ash-based high-sulfur-fixation coal binder and preparation method and application thereof |
| CN114437367A (en) * | 2022-02-25 | 2022-05-06 | 云南旭光节能有限公司 | Method for producing potassium humate by utilizing lignite humic acid |
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