CN100412166C - Coal additive and method for raising coke output and performance - Google Patents
Coal additive and method for raising coke output and performance Download PDFInfo
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- CN100412166C CN100412166C CNB2006101147494A CN200610114749A CN100412166C CN 100412166 C CN100412166 C CN 100412166C CN B2006101147494 A CNB2006101147494 A CN B2006101147494A CN 200610114749 A CN200610114749 A CN 200610114749A CN 100412166 C CN100412166 C CN 100412166C
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Abstract
The present invention relates to coal additive and method for raising coke output and performance. The coal additive contains surface activating catalyst, co-solvent, permeation assistant and solvent. When the coal additive is used, the surface activating catalyst is dissolved in the solvent, added into coal through a specific mode, and distributed on the surface of coal and inside coal under the action of the permeation assistant. During producing coke, the coal additive is heated and the volatile component is separated out, to raise the output and performance of the produced coke. The high performance coke may be used in coal burning, dry distilling, gasifying, liquefying and other fields. The present invention can reach the aims of raising the utilization rate of coal, saving coal resource, reducing pollutant, etc.
Description
Technical field
The invention belongs to novel save energy technical field, relate to a kind of coal additive and method that improves coke output and performance.
Background technology
The energy is the basic substance of the development of the national economy.The primary energy source coal of China is main, and the proportion of coal in the primary energy source demand is about 70%.In the coal total amount that China consumes, be directly used in direct incendiary coal such as thermal power generation, Industrial Boiler, Industrial Stoves and family's cooking stove according to statistics up to more than 85%.But owing to traditional cause China's energy supply and demand contradiction sharp-pointed with coal mode, low-level efficiency of combustion, efficiency of energy utilization is low, and energy technology falls behind, and the major industrial product unit consumption of energy country of emulating the advanced exceeds 20-50%.Simultaneously, because a large amount of directly burnings of coal have directly caused the serious coal-burning topsoil of China, be the main source of sulfurous gas in the atmospheric environment, oxynitride, flue dust, the environment of China has been caused havoc, also directly caused the serious burning type topsoil of China.From the whole service condition of coal, mainly comprise coal burning, coal destructive distillation, gasification of coal and coal liquefaction.Wherein, these four kinds of coals use in its process and all inevitably will that is to say that the yield from coal to the coal tar and the performance of coal tar will play a crucial role for the whole service efficiency of coal through this form of coal tar or semicoke.Therefore, exploitation can improve the technology of coal tar output and performance, plays an important role for improving resource utilization, coal overall utilization and alleviating environmental pollution.
The research of at present existing a large amount of clean energy-saving utilisation technology aspects about coal as purificant, catalysis burning-rate accelerator, purification agent etc., in the hope of improving the performance of coal, improves combustion position, reduces the discharging of combustion tail gas and lime-ash.Its mechanism of improving combustion position is to use oxygen to transmit theory and transfer transport theory ([1] Xiao Jianli, Kang Hua, Wang Zhenyang, the discussion of coal combustion catalyst catalytic mechanism, " coal technology ", 2002,21 (11): 73～75.[2] horse development, Zhao Hongbin, Dong Zhenqiang, coal combustion catalyst, " boiler technology ", 2000,31 (4): 5～7.[3] MckeeDW, Mechanisms of the aikalimetai catalysedgasification of carbon, " Fule ", 1983,62 (2): 170～175.[4] horse development, Guo Xingxiu, Li Jing, Han Ailing, the research of coal combustion catalyst and application, " heat energy is learned and engineering ", 2001,16 (6): 579～581.[5] Patrick JW, Walker AA, Study of the copper-catalyed combustion of carbon, " Carbon ", 1974,12 (5): 507～515.), and this class research mainly concentrates on the salt and oxide compound of basic metal, alkaline-earth metal and transition metal.Existing all kinds of coal catalyst and additive are to improving the performance of coal, improve combustion position, it is more or less all helpful to reduce the discharging of combustion tail gas and lime-ash, but because also there are many problems really in the aspects such as security, stability, economy and production operability of practical effect, use, cause negative factor to be difficult to greatly promote, also occur the good product of energy large-scale application so far.In addition, it is to lay particular emphasis on to reduce the coal point of ignition and improve coal low volatile content that these researchs have great majority, thus not too many to the raising of whole burning of coal efficient, and otherwise application seldom relates to for coal.
Field in coal consumption maximum---coal burning field, general theory is thought, in combustion processes, begin to be subjected to heated drying, volatile matter to be released to the most of burning-out of volatile matter from coal, approximately only account for 10% of coal total combustion time, and coke (remainder after coal drying, volatile matter disengage) accounts for the last 90% combustion time.On the other hand, the flammable matter content of coke accounts for 55～97% of coal total amount in the coal, the thermal value of coke accounts for 60～95% (" Theory of Combustion with pollute control " Cen Kefa, Yao Qiang, Luo Zhong determine, write the Gao Xiang, 2004 June the 1st edition) of coal total calorific value.Therefore no matter from combustion time, the quantity of burning with emit heat, the burning of coke all is topmost in the burning of coal process, can think that burning of coal mainly is the burning of coke.Therefore combustionvelocity, combustionproperty and the heat output of coke are determining combustionvelocity, performance and the heat of whole coal.That is to say that the output of coal tar and the raising of performance are significant for the energy efficiency of Application Areass such as coal burning, coal destructive distillation, gasification of coal and coal liquefaction.Based on the urgent present situation of the current energy of China and environmental protection, research and develop out the technology that can improve coal tar output and performance, just seem particularly important for improving coal resources utilization ratio, coal overall utilization and alleviating environmental pollution.
Summary of the invention
Technical problem to be solved by this invention is: solve the committed step in the coal application, promptly develop the technology that improves coal tar output and coal tar performance, and be applied to fields such as coal burning, coal destructive distillation, gasification of coal and coal liquefaction, in the hope of reaching the performance that improves coal, improve burning or production status, reduce dischargings such as combustion tail gas and lime-ash, realize improving the coal overall utilization, economize on resources and alleviating technology and society targets such as environmental pollution.
The technical solution used in the present invention is as follows: the method for raising coke output of the present invention and performance is that the help of suitable surface active catalyzer by dissolution aids is dissolved in the oiliness solvent, add in the coal by specific mode, can be under the effect of penetrant at coal surface and inner uniform distribution.After process heat drying and volatile matter are separated out, obtain high yield and high performance coke, this high performance coke can be applicable to a plurality of fields such as coal burning, destructive distillation, gasification and liquefaction.Also can directly above-mentioned oily matter and other coal that contains surface active catalyzer, dissolution aids and penetrant be answered used additives or catalyzer, as desulfurization catalyst, nitrogen oxide catalyst, gasifying catalyst and deliquescence accelerant etc. altogether molten after, add in the coal by specific mode, directly use, speed of response and productive rate are improved, reach purposes such as improving coal utilizaton rate, saving coal resources, minimizing pollutent, safe and efficient production.
Employed surface active catalyzer is selected from one or more in the sodium, potassium, aluminium, zinc, iron, cobalt, nickel salt of the complex compound of part such as the diphenylpropane-1,3-dione(DPPO), methyl ethyl diketone, methyl aceto acetate, oxalic acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), phenanthroline, acetyl thiophene, cyclopentadiene of aluminium, zinc and iron and naphthenic acid etc., preferred aluminium acetylacetonate, ferrocene and sodium napthionate.Content is 0.01%～10.0%, preferred 0.1%～3.0%.
Employed dissolution aids is selected from tetrachloroethane, trichloropropane, triglycol dichloride, Tetraglycol 99 dichloride, dichlorobenzene, trichlorobenzene, N-hydroxyformamide, Lactoyl amine, N hydroxymethyl acrylamide, acrylamide, N, dinethylformamide, N, in N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), acetyl thiophene, dodecyl sodium sulfonate, dodecyl sulphate, octadecyl sulfonic acid, the p-methyl benzenesulfonic acid etc. one or more, preferred N, dinethylformamide, dimethyl sulfoxide (DMSO) and dodecyl sodium sulfonate.Content is 0.05%～20.0%, preferred 0.5%～5.0%.
Employed oiliness solvent is selected from diesel oil, heavy oil, residual oil, turps, paraffin oil, one or more in white oil of camphor, edible oil, various industry and the life waste oil etc., preferred diesel oil, heavy oil, edible oil.Content is 55%～99.93%, preferred 85%～95%.
Employed penetrant is selected from stearic acid, phenylformic acid, styracin, oxalic acid, propanedioic acid, toxilic acid, phthalic acid, R-Glyceric acid, the methyl esters of propionic acid etc., ethyl ester, propyl ester, butyl ester, pentyl ester, the second diester, the butoxy ethyl ester, glyceryl ester, sorbitol ester, phenyl ester, benzyl ester and polyoxyethylene carboxylate, polyoxyethylenated castor oil, polyoxyethylene polyoxypropylene monobutyl ether, polyoxypropylene-polyoxyethylene glycerin ether, the Zhong Xin polyoxyethylenated alcohol, alkyl-polyoxyethylene ether acetate, polyoxyethylene lauryl sulfate triethanolamine salt, AESA, aliphatic acid polyethenoxy ether, styryl phenol Soxylat A 25-7, emulsifier BP, alkylphenol polyoxyethylene, sorbitol polyoxyethylene ether, polyoxyethylene sorbitol acid anhydride three hard ester acid esters, Tween-20, the sorbitol anhydride mono-laurate, TWEEN40, polyoxyethylene (4) sorbitan single-hard ester acid ester, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol acid anhydride list hard acid ester, polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether, dimethyl silicone oil, phenyl silicone oil, in the chloro-phenyl-silicone oil etc. one or more.Preferred stearic acid glyceryl ester, fatty alcohol-polyoxyethylene ether and dimethyl silicone oil.Content is 0.01%～15.0%, preferred 0.1%～5.0%.
Kind, kind, quality and application art operating mode and service requirements according to coal, surface active catalyzer, dissolution aids and the penetrant of choosing different ratios are dissolved in the solvent, other coals be can add in addition and used additives or catalyzer answered, as desulfurization catalyst, nitrogen oxide catalyst, gasifying catalyst and deliquescence accelerant etc., be prepared into homodisperse solution or milk sap.During use, form aerosol with high-pressure jet device or air-atomizing device, atomizing droplet is generally less than 10 microns, preferably less than 2 microns.Coal feedstock is contacted with aerosol, guarantee that oiliness improver can be to greatest extent and all coal particles surface arrangement.Under the effect of penetrant, the surface active catalyst entrainment can be advanced on coal particles inside and the internal surface again, guarantee the surperficial and fully dispersion of inside in coal feedstock to greatest extent, thereby bring into play maximum catalytic effect in the catalyzed reaction afterwards.
The oiliness improver addition is 0.1/10000th～50 of a coal weight, preferred 0.5/10000th to 20.
Coal after the interpolation uses after back 1 minute to 24 hours in interpolation, preferred 30 minutes to 4 hours, guarantees that catalyzer is in the inner fully dispersion of coal, performance best effects.
Coal feedstock after the interpolation obtains the coke of high-specific surface area and high surface through coking, and specific surface area improves 20% to 200%, and surfactivity improves 50% to 500%, and the coal tar yield improves 10% to 30%.When the coal feedstock after adding directly was used in coal burning, destructive distillation, gasification and liquefaction etc., general speed of response improved 20% to 300%, and the total service efficiency of coal improves 10% to 50%.
Know-why of the present invention:
The rock that coal is made up of multiple organic micropetrological unit, inorganic mineral and clay.Except containing water and mineral substance (ash content), it is flammable He can utilize composition mainly is carbon and hydrogen, and constitutes organic polymer together with contained a small amount of oxygen, nitrogen, sulphur.Coal is mixed by the organic polymer particle that contains C, H, O, N, S of a lot of different structures and dirt and is combined into whole.Between various organic polymer particles, often connect to bigger particle mutually by different hydrocarbon side chains.Be mingled with various impurity between the macroparticle, or leaving tiny hole and slit.
Coal is when being heated, and the moisture in coal grain surface and the slit evaporates gradually and becomes the exsiccant coal.The chain or the ring-type volatile hydrocarbons of easy fracture are come out, that is have volatile matter to discharge.The release rate of volatile matter is closely related with the characteristic of coal, Heating temperature and speed.If volatile matter that discharges and oxygen meet, just take fire when reaching ignition condition.Make after the difficult hydrocarbonize platform thing that decomposes is also separated out, volatilized in the coal when temperature continue to raise, similar that left is exactly is in graphite, the coke of being made up of a lot of tiny crystal grains.
Physics distillation and pyrolytic decomposition (and recombine) that the process that is subjected to the thermosetting coke of coal comprises component have only a decomposition course concerning coal itself.In pyrolytic process, inflammable gas is emitted with carbonic acid gas and water, according to the composition and the pyrolytical condition of coal, produces the condensable oils and the tar of different amounts, oxygenatedchemicals and hydrocarbon polymer are wherein arranged, and mainly are various aromatic compounds and the aromatic compound that contains branched structure.And remaining solid just forms coke.
The output of coke and performance be except with coal and production control process are directly related, also with coal in, especially the performance of surfaces externally and internally is directly related.Industrial practice shows, adds ZnCl in process of coking
2, AlCl
3, NaOH, H
3PO
4, atlapulgite, ferric oxide or gac be for reducing tar output, improves coal tar output and gas yield (H
3P0
4Except gac), improve the ratio of carbon-hydrogen in the low volatile, and can improve the performance (" conversion of coal ") of coke to a certain extent.On mechanism, mainly be by the metal ion that catalysis is arranged, comprise that the coal internal portion forms the metal ion of ash content, low volatile in catalytic pyrolysis and the reformation coal produces the hydrocarbon polymer of more amount, has reduced the output of tar.Because the generation of more lower molecular weight hydrocarbon polymer remains more high ratio of carbon-hydrogen compound and coke.Simultaneously, because the minimizing of the coal-tar middle oil material of coal, the coke ratio surface-area increases and partly forms the activation of the metal ion case of ash content, makes the performance of coke be improved.
From as seen last, suitably add metallic compound with catalysis and the compound that can excite the inner ash content metal ion of coal, just can effectively improve coke output and performance.Based on this understanding, the inventor has mainly carried out innovation on selection of catalysts and using method.Select the metallic compound and the method that these metallic compounds can be distributed to the coal surfaces externally and internally of excellent surface activating catalytic effect for use.As everyone knows, the catalytic effect of catalyzer is long-pending directly related with catalytic reaction surface, and therefore improving the reaction table area just can improve the catalyzed reaction effect.
At present the various coal class catalyzer of bibliographical information or the addition manner of additive have following several: 1) solid catalyst is directly sneaked into the mode among the coal, because the dispersion of catalyzer is even inadequately, the catalyzed reaction area is little, cause katalysis the poorest, both made the increase addition also be difficult to obtain significantly to improve effect.2) spray the addition manner of aqueous catalyst solution and compare with the direct mode of sneaking into, the be uniformly dispersed degree of catalyzer in coal is improved to a certain extent, and the reaction contact area of catalyzer and coal has had raising, and catalytic effect has obtained more significantly raising.But because the coal surface is oil loving, this addition manner can not guarantee that catalyzer disperses fully in coal, especially coal inside.3) addition manner of the coal impregnated catalyst aqueous solution is spraying on the basis of adding, and further improved the degree of scatter and the reaction contact area of catalyzer, thereby catalytic effect is further enhanced.In like manner, this addition manner can not guarantee the dip operation space that catalyzer disperses fully and need be bigger in coal, and has strengthened the burden of producing.4) the addition manner catalytic effect of ion-exchange is best, and this mode has really realized the chemisorption of catalyzer and coal.But this needs multitasking, the cost height, and the secondary pollution of ion-exchange is big, and real catalytic effect is limited.
The present invention selects the metallic compound of excellent surface activating catalytic effect for use, can form uniform solution and emulsion with the oiliness solvent under the dissolution aids effect.Adopted unique spraying addition manner, can guarantee that minimum addition contacts with the coal fullest with effective constituent.Owing to the oiliness of solvent itself, add the effect of penetrant, can fast and effectively metallic compound be carried into coal inside, reach and bring into play the activating catalytic effect to greatest extent.Output and the performance that improves coal tar there is obvious effects.Answering used additives or catalyzer with other coals, as associatings such as desulfurization catalyst, nitrogen oxide catalyst, gasifying catalyst and deliquescence accelerants, directly be used in coal burning, destructive distillation, gasification and liquefaction etc., speed of response improves, the total service efficiency of coal improves, and can reach the requirement of environmental protection and production safety simultaneously.
The inventive method is compared with other kinds coal additive, and the present invention has following advantage:
1) the raw material great majority of the present invention's employing are conventional industrial chemicals, can guarantee the big area life-time service;
2) all raw materials of the present invention's employing do not contain inflammable and explosive dangerous goods, and it is convenient with transportation safety to be mixed, and cost is low, and addition is few;
3) the present invention adopts the addition manner of spraying, can be used in various boilers, reaction bed and conversion unit, can add in the process of adding coal former (combustion) material, need not change original technology and flow process, and is easy and safe to operate;
4) the inventive method effect is obvious, and the coke ratio surface-area that obtains improves 20% to 200%, and surfactivity improves 50% to 500%, and the coal tar yield improves 10% to 30%;
5) the inventive method can with other multiple coal catalysts and the supporting use of catalyst for additives, be free from side effects, synergy is obvious, general speed of response improves 20% to 300%, the total service efficiency of coal improves 10% to 50%;
6) all raw materials of the inventive method employing do not contain heavy metal and radioelement, do not contain highly toxic substance, can not bring secondary pollution problems;
7) amount of the inventive method interpolation is few, and effect is obvious, for economizing on resources, save the productive labor cost, enhance productivity and guarantee that production safety all has good effect.
Embodiment
Embodiment 1
1 part of aluminium acetylacetonate, 1 part of ferrocene, 1 part of sodium napthionate, N, 3 parts of dinethylformamides, 1 part of dimethyl sulfoxide (DMSO), 1 part of dodecyl sodium sulfonate, 1 part of stearic acid glyceryl ester, 1 part of diphenyl phthalate, 1 part of dimethyl silicone oil, 200 parts of diesel oil, 50 parts in heavy oil.Aluminium acetylacetonate, ferrocene, sodium napthionate, dodecyl sodium sulfonate, stearic acid glyceryl ester, diphenyl phthalate and dimethyl silicone oil are joined N successively, in dinethylformamide and the dimethyl sulphoxide solution, stir fast, obtain milk sap, stir fast on one side, Yi Bian add diesel oil.Diesel oil adds the back and adds heavy diesel, fully stirs and obtains half settled solution, and a small amount of insolubles is arranged, and filters, and clear liquid is the coke additive.
Get 40 tons in hard coal, 35 tons in bituminous coal, 25 tons in coking coal, be crushed to granularity and then three kinds of raw coal mixed less than 5mm, the coke additive is added in the ratio spraying by weight 1: 1000 when entering pulverizer, is crushed to granularity again less than 3mm, obtain coking coal, caking index is 43, fugitive constituent 25%, Y value 1.68.Coking coal is drawn fixing apparatus by hydraulic pressure draw solid moulding, degree of compactness reaches 1.03～1.09, goes into stove destructive distillation coking.Coking yield improves 10～30%, and the coke ratio surface-area improves 20～200%, and surfactivity improves 50～500%.
Embodiment 2
3 parts of diphenylpropane-1,3-dione(DPPO) iron, 1 part of ironic oxalate, 1 part on EDTA zinc, 1 part of nickel naphthenate, 3 parts of tetrachloroethane, 3 parts of trichloropropanes, 3 parts of triglycol dichloride, 3 parts of Tetraglycol 99 dichloride, methyl benzoate, ethyl cinnamate, oxalic acid propyl ester, each 1 part of propanedioic acid butyl ester, 1 part of polyoxyethylene carboxylate, 1 part of phenyl silicone oil, 3 parts of desulphurization and denitrification catalysts, 500 parts of edible soybean oils, 100 parts of waste cooking oils.Diphenylpropane-1,3-dione(DPPO) iron, ironic oxalate, EDTA zinc, nickel naphthenate, methyl-formiate, ethyl cinnamate, oxalic acid propyl ester, propanedioic acid butyl ester, polyoxyethylene carboxylate, phenyl silicone oil and desulphurization and denitrification catalyst are joined in tetrachloroethane, trichloropropane, triglycol dichloride and the Tetraglycol 99 dichloride solution successively, stir fast, obtain milk sap, stir fast on one side, Yi Bian add edible soybean oil.Diesel oil adds the back and adds waste cooking oil, fully stirs and obtains half settled solution, and a small amount of insolubles is arranged, and filters, and obtains clear liquid, is coal combustion catalyst.
During use, add coal combustion catalyst to coal fuel, add, add the back and directly advanced the stove burning in static 1～24 hour than 2/10000ths by the mode of spraying.Efficiency of combustion improves 5～20%, and coal saving rate is 10～40%, and black smoke obviously reduces, and the discharging of sulfurous gas and oxynitride reduces 20～40%, no coking in the stove.
Embodiment 3
1 part of acetyl thiophene iron, 1 part of sodium napthionate, 1 part of cyclic potassium naphthenate, 1 part of aluminum napthenate, 1 part of magnesium naphthenate, 3 parts of N-hydroxyformamides, 3 parts of Lactoyl amine, 3 parts of N hydroxymethyl acrylamides, 3 parts of acrylamides, each 0.5 part of polyoxyethylene carboxylate, polyoxyethylenated castor oil, polyoxyethylene polyoxypropylene monobutyl ether and polyoxypropylene-polyoxyethylene glycerin ether, 1 part of phenyl silicone oil, 100 parts of diesel oil, 300 parts of paraffin oils.Acetyl thiophene iron, sodium napthionate, cyclic potassium naphthenate, aluminum napthenate, magnesium naphthenate, polyoxyethylene carboxylate, polyoxyethylenated castor oil, polyoxyethylene polyoxypropylene monobutyl ether and polyoxypropylene-polyoxyethylene glycerin ether and phenyl silicone oil are joined in N-hydroxyformamide, 3 parts of Lactoyl amine, N hydroxymethyl acrylamide and the acrylamide soln successively, stir fast, obtain milk sap, stir fast on one side, on one side the edible diesel oil of adding.Diesel oil adds the back and adds paraffin oil, fully stirs and obtains half settled solution, and a small amount of insolubles is arranged, and is the gac deactivated catalyst.
Feed coal is pulverized,, added the gac deactivated catalyst of being joined to fine coal, add, stir and guarantee fully contact than 8/10000ths by the mode of spraying less than 100 orders.Draw fixing apparatus with hydraulic pressure and draw solid moulding, the secret room degree reaches 1.03～1.09, goes into stove destructive distillation coking.Jiao pulverizes, and less than 100 orders, goes into stove and carry out carbonization and activation treatment (20 ℃/min of heat-up rate in nitrogen atmosphere, temperature is 800 ℃ eventually, activates 2 hours), the gac yield improves 15～50%, the charcoal specific surface area improves 40～100%, and surfactivity improves 100～500%.
Embodiment 4
1 part of oxalic acid iron, 1 part in EDTA aluminium sodium, 1 part of cobalt naphthenate, 1 part of nickel naphthenate, 1 part of magnesium naphthenate, N, 3 parts of N-N,N-DIMETHYLACETAMIDEs, 3 parts of dimethyl sulfoxide (DMSO), 3 parts of acetyl thiophenes, 3 parts of dodecyl sodium sulfonates, the Zhong Xin polyoxyethylenated alcohol, alkyl-polyoxyethylene ether acetate, polyoxyethylene lauryl sulfate triethanolamine salt, AESA, aliphatic acid polyethenoxy ether, styryl phenol Soxylat A 25-7, each 0.5 part of emulsifier BP and alkylphenol polyoxyethylene, 1 part of chloro-phenyl-silicone oil, 5 parts of gasification of coal catalyzer, 50 parts in residual oil, 500 parts in turps.With oxalic acid iron, EDTA aluminium sodium, cobalt naphthenate, nickel naphthenate, magnesium naphthenate, dodecyl sodium sulfonate, the Zhong Xin polyoxyethylenated alcohol, alkyl-polyoxyethylene ether acetate, polyoxyethylene lauryl sulfate triethanolamine salt, AESA, aliphatic acid polyethenoxy ether, styryl phenol Soxylat A 25-7, emulsifier BP and alkylphenol polyoxyethylene, chloro-phenyl-silicone oil and gasification of coal catalyzer join N successively, the N-N,N-DIMETHYLACETAMIDE, in the solution of dimethyl sulfoxide (DMSO) and acetyl thiophene, stir fast, obtain milk sap, stir fast on one side, Yi Bian add turps.Diesel oil adds the back and adds residual oil, fully stirs and obtains half settled solution, and a small amount of insolubles is arranged, and is the gasification of coal catalyzer.
Feed coal is pulverized,, added the gasification of coal catalyzer of being joined to fine coal, add, stir and guarantee fully contact than 5/10000ths by the mode of spraying less than 100 orders.Enter the lurgi gasifier gasification after static 2～8 hours, obtain domestic gas.H2, CH4 and other hydro carbons inflammable gas content raising 2～20% does not wait in the coal gas, and calorific value improves 5～30%, and CO reduces 10～50%.
Embodiment 5
1 part on methyl aceto acetate zinc, 3 parts of cobalt naphthenates, 1 part of nickel naphthenate, 1 part of aluminum napthenate, 5 parts of trichloropropanes, 3 parts of acrylamides, 2 parts of octadecyl sulfonic acid, each 0.5 part of sorbitol polyoxyethylene ether, polyoxyethylene sorbitol acid anhydride three hard ester acid esters, Tween-20, sorbitol anhydride mono-laurate, TWEEN40 and polyoxyethylene (4) sorbitan single-hard ester acid ester, 1 part of dimethyl silicone oil, 5 parts of coal liquefaction catalyzer, 100 parts of diesel oil, 400 parts of white oil of camphor.With methyl aceto acetate zinc, cobalt naphthenate, nickel naphthenate, aluminum napthenate,, octadecyl sulfonic acid, sorbitol polyoxyethylene ether, polyoxyethylene sorbitol acid anhydride three hard ester acid esters, Tween-20, sorbitol anhydride mono-laurate, TWEEN40, polyoxyethylene (4) sorbitan single-hard ester acid ester, dimethyl silicone oil and coal liquefaction catalyzer join in trichloropropane and the acrylamide soln successively, stir fast, obtain milk sap, stir fast on one side, Yi Bian add diesel oil.The oil that camphorates after diesel oil adds fully stirs and obtains half settled solution, and a small amount of insolubles is arranged, and is the coal liquefaction catalyzer.
Feed coal is pulverized,, added the gasification of coal catalyzer of being joined to fine coal, add, stir and guarantee fully contact than 5/10000ths by the mode of spraying less than 100 orders.Enter the liquefaction of liquefaction stove, reaction conditions is 350～450 ℃, and the initial hydrogen dividing potential drop is 5～25Mpa, and transformation efficiency improves 10～50%, and the reaction times reduces 20～200%, and liquefied fraction improves 20～50%.
Embodiment 6
3 parts of oxalic acid iron, 3 parts of sodium napthionates, 1 part of aluminum napthenate, 3 parts of N-hydroxyformamides, 3 parts of Lactoyl amine, 3 parts of N hydroxymethyl acrylamides, 3 parts of acrylamides, each 0.5 part of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol acid anhydride list hard acid ester, polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and dimethyl silicone oil, 500 parts of diesel oil.Oxalic acid iron, sodium napthionate, aluminum napthenate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol acid anhydride list hard acid ester, polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and dimethyl silicone oil are joined in N-hydroxyformamide, Lactoyl amine, N hydroxymethyl acrylamide and the acrylamide soln successively, stir fast, obtain milk sap, stir fast on one side, Yi Bian add diesel oil.Fully stir and obtain half settled solution, a small amount of insolubles is arranged, be the honeycomb briquette combustioncatalysts.
During use, mix the back standing over night with coal dust by the mode of spraying.Add clay then, mold pressing is a honeycomb briquette behind the mixings such as water, dries the back and uses.This improved honeycomb briquette point of ignition is low, catches fire easily, and the flame cyan, obnoxious flavoures such as burning back carbon monoxide and sulfurous gas are few, are the good heating raw materials in rural area or suburb, cities and towns.
Claims (13)
1. coal additive that improves coal tar output and coal tar performance, it comprises: the surface active catalyzer, dissolution aids, penetrant and oiliness solvent, the content of described surface active catalyzer is 0.1%～3.0%, the content of penetrant is 0.1%～5.0%, and the content of dissolution aids is 0.5%～5.0%, and the content of oiliness solvent is 85%～95%; Wherein said oiliness solvent is selected from diesel oil, heavy oil, turps, paraffin oil, one or more in white oil of camphor, edible oil, industrial waste oil and the life waste oil; Described surface active catalyzer is selected from one or more in complex compound and the naphthenate, and wherein complex compound is: one or more in the diphenylpropane-1,3-dione(DPPO) of aluminium, zinc or iron, methyl ethyl diketone, methyl aceto acetate, oxalic acid, EDTA, phenanthroline, thiophene or the cyclopentadiene complex; Naphthenate is: one or more in the sodium of naphthenic acid, potassium, calcium, magnesium, aluminium, iron, zinc, cobalt or the nickel salt.
2. the described coal additive of claim 1, wherein said oiliness solvent is selected from diesel oil, heavy oil and/or edible oil.
3. the described coal additive of claim 1, wherein said industrial waste oil is a residual oil.
4. coal additive as claimed in claim 1, wherein said surface active catalyzer is aluminium acetylacetonate, ferrocene and sodium napthionate.
5. coal additive as claimed in claim 1, it is characterized in that: described dissolution aids is selected from tetrachloroethane, trichloropropane, triglycol dichloride, Tetraglycol 99 dichloride, dichlorobenzene, trichlorobenzene, N-hydroxyformamide, Lactoyl amine, N hydroxymethyl acrylamide, acrylamide, N, in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), acetyl thiophene, dodecyl sodium sulfonate, dodecyl sulphate, octadecyl sulfonic acid and the p-methyl benzenesulfonic acid one or more.
6. coal additive as claimed in claim 5, wherein said dissolution aids is selected from N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO) and the dodecyl sodium sulfonate.
7. coal additive as claimed in claim 1, it is characterized in that: described penetrant is selected from stearic acid, phenylformic acid, styracin, oxalic acid, propanedioic acid, toxilic acid, phthalic acid, the methyl esters of R-Glyceric acid or propionic acid, ethyl ester, propyl ester, butyl ester, pentyl ester, the second diester, the butoxy ethyl ester, glyceryl ester, sorbitol ester, phenyl ester or benzyl ester, polyoxyethylene carboxylate, polyoxyethylenated castor oil, polyoxyethylene polyoxypropylene monobutyl ether, polyoxypropylene-polyoxyethylene glycerin ether, the Zhong Xin polyoxyethylenated alcohol, alkyl-polyoxyethylene ether acetate, polyoxyethylene lauryl sulfate triethanolamine salt, AESA, aliphatic acid polyethenoxy ether, styryl phenol Soxylat A 25-7, emulsifier BP, alkylphenol polyoxyethylene, sorbitol polyoxyethylene ether, polyoxyethylene sorbitol acid anhydride three hard ester acid esters, Tween-20, the sorbitol anhydride mono-laurate, TWEEN40, polyoxyethylene sorbitol acid anhydride single-hard ester acid ester, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, fatty alcohol-polyoxyethylene ether, dimethyl silicone oil, one or more in phenyl silicone oil and the chloro-phenyl-silicone oil.
8. coal additive as claimed in claim 7, wherein said penetrant is selected from one or more in stearic acid glyceryl ester, fatty alcohol-polyoxyethylene ether and the dimethyl silicone oil.
9. as each described coal additive among the claim 1-8, it is characterized in that: wherein also contain desulphurization and denitrification catalyst, gasification of coal catalyzer and/or coal liquefaction catalyzer.
10. method that is used to improve coal tar output and coal tar performance as each described coal additive among the claim 1-9, it comprises the steps: each described coal additive among the claim 1-9 is added in the coal, wherein said coal additive forms aerosol with high-pressure jet device or air-atomizing device and adds in the coal, and the atomizing droplet of described aerosol is less than 10 microns.
11. method according to claim 10 is characterized in that: the atomizing droplet of aerosol is less than 2 microns.
12. according to claim 10 or 11 described methods, it is characterized in that: described additive addition is 0.1/10000th～50 of a coal weight.
13. method according to claim 12 is characterized in that: described additive addition is 0.5/10000th to 20 of a coal weight.
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| CN103194293B (en) * | 2012-01-09 | 2015-02-18 | 张春山 | Method for improving combustion speed of coal |
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| CN107201242A (en) * | 2017-06-28 | 2017-09-26 | 徐州市龙山制焦有限公司 | A kind of coking additire and preparation method thereof |
| CN109609239A (en) * | 2018-11-29 | 2019-04-12 | 亿利洁能科技（颍上）有限公司 | A method of improving coal burning speed |
| CN110387280A (en) * | 2019-08-15 | 2019-10-29 | 南宁方力电气有限公司 | A kind of coal combustion clean catalysis agent |
| CN112175688B (en) * | 2020-10-22 | 2022-03-25 | 安徽海螺新材料科技有限公司 | Cement clinker calcination fire coal additive and preparation method thereof |
| CN113040140B (en) * | 2021-01-28 | 2022-06-03 | 菲吉乐科(南京)生物科技有限公司 | Auxiliary penetrating agent suitable for bacteriophage to be immersed into lianas and woody plants and preparation method and application thereof |
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