CN204529700U - A kind of system utilizing fine coal preparing ethylene - Google Patents
A kind of system utilizing fine coal preparing ethylene Download PDFInfo
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- CN204529700U CN204529700U CN201520317245.7U CN201520317245U CN204529700U CN 204529700 U CN204529700 U CN 204529700U CN 201520317245 U CN201520317245 U CN 201520317245U CN 204529700 U CN204529700 U CN 204529700U
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Abstract
The utility model belongs to coal chemical technology, a kind of system utilizing fine coal preparing ethylene is proposed, comprise pyrolysis upgrading unit, pressure-variable adsorption carries hydrogen unit, smelt and produce calcium carbide unit, CO conversion decarburization Hydrogen Unit, carbide-feed generator, acetylene hydrogenation reaction member paste state bed reactor, low temperature separation process unit and carbide slag carbonation unit; Pyrolysis upgrading unit comprises pyrolysis installation, is provided with conduit and is connected with institute furnace of calcium carbide bottom described pyrolysis installation; Pyrolysis installation top has pyrolysis gas escape route connection pressure-variable adsorption to carry hydrogen unit; Acetylene hydrogenation reaction member comprises paste state bed reactor.The utility model can use cheap middle low order powdery raw coal, the system proposed, and has that flow process is short, floor space is few, energy consumption is low, a less investment and reduce CO
2the advantages such as discharge, in the gaseous products of generation, ethene accounts for 75 ~ 85%, anti-butylene account for 15 ~ 20% all the other be the by product such as ethane, propylene and C5+, after reaction, gas is after low temperature separation process, and hydrogen recycle uses.
Description
Technical field
The utility model belongs to coal chemical technology, is specifically related to a kind of system of fine coal preparing ethylene.
Background technology
Ethene is a kind of main raw material of petrochemical industry, and huge demand has consolidated its importance further.2015-2020 world Ethylene production capacity speedup will be increased to about 4.1%, and demand speedup then brings up to 4.0%, and demand is suitable with production capacity speedup, and device working rate is suitable.Within 2015, domestic ethene aggregated capacity will reach about 2,200 ten thousand t/a, the domestic ethene production capacity of the year two thousand twenty is increased to 3,250 ten thousand t/a further, expecting the domestic ethene consumption of the year two thousand twenty is 4,800 ten thousand tons, demand is greater than production capacity, and this defines serious strategy threat for China that oil reserve is not enriched.Therefore, seek another kind of new source and processing method prepares large basic organic chemical raw material-ethene, at field of industrial production petroleum replacing as raw material, the dependency of China for oil can be alleviated to a great extent.The ethylene production route that positive active development raw material sources are abundanter both at home and abroad, wherein the synthetic gas methanol of coal-based or Sweet natural gas base or dme produce the low-carbon alkene technique based on ethene and propylene, but above-mentioned Technology long flow path, complex process, investment are greatly, and the demand especially for water causes greatly cannot carrying out in the region of lack of water.
Coal resources in China rich reserves, low-rank coal account for China proven reserve 55%, wherein brown coal account for 13% of total amount, and long-flame coal, weakly caking coal, non caking coal etc. are lower-grade metamorphic bituminous accounts for 42% of total amount.It is low that low-rank coal has carbon content, and moisture is high, and volatile matter is high, easy efflorescence spontaneous combustion, and the features such as immersion, dropping strength difference, are not suitable for long-distance sand transport, limit the direct utilization of low-rank coal, constrains the trans-utilizations such as its liquefaction, gasification and destructive distillation.If will can obtain the multiple coal-based product such as semicoke, coal tar oil and gas of high-quality after low order improving quality of coal by pyrolysis, improve reliability and the utilization ratio of low-rank coal, have technique simple, construction investment is few, and production cost is low, and product such as can to fully utilize at the feature.
Utility model content
For the deficiencies in the prior art part, the utility model provides a kind of system utilizing fine coal preparing ethylene.
Realizing the utility model object technical scheme is:
Utilize a system for fine coal preparing ethylene, comprise pyrolysis upgrading unit, pressure-variable adsorption carries hydrogen unit, smelt and produce calcium carbide unit, CO conversion decarburization Hydrogen Unit, acetylene generating unit, acetylene hydrogenation reaction member and low temperature separation process unit;
Described pyrolysis upgrading unit comprises pyrolysis installation, and described pyrolysis installation is provided with pyrolysis gas outlet and discharge port, and described pyrolysis gas outlet connects described pressure-variable adsorption and carries hydrogen unit;
Described pressure-variable adsorption is carried hydrogen unit and is provided with hydrogen outlet;
Described smelting is produced calcium carbide unit and is comprised furnace of calcium carbide, and described furnace of calcium carbide is provided with opening for feed and offgas outlet, and the opening for feed of described furnace of calcium carbide is connected with the discharge port of described pyrolysis upgrading unit;
CO conversion decarburization Hydrogen Unit is provided with inlet mouth, hydrogen outlet and CO
2outlet, the inlet mouth of described CO conversion decarburization Hydrogen Unit is connected with the offgas outlet of described furnace of calcium carbide; The inlet mouth of described CO conversion decarburization Hydrogen Unit is also connected with steam-pipe;
Described acetylene hydrogenation reaction member comprises paste state bed reactor, described paste state bed reactor is provided with acetylene import, product gas outlet, and the hydrogen outlet that described pressure-variable adsorption carries hydrogen unit is all connected with the hydrogen outlet of described CO conversion decarburization Hydrogen Unit the hydrogen pipeline entering paste state bed reactor; The acetylene import of described paste state bed reactor connects described acetylene generating unit; Described product gas outlet connects described low temperature separation process unit;
Described acetylene generating unit is provided with carbide slag outlet.
Further, described system also comprises carbide slag carbonation unit, and the carbide slag outlet of described carbide-feed generator connects described carbide slag carbonation unit, the CO of described CO conversion decarburization Hydrogen Unit
2outlet connects described carbide slag carbonation unit.
Wherein, described pressure-variable adsorption carry hydrogen unit comprise connect in turn chilling device, primary cooler, gas-liquid separator, electrical tar precipitator, wash benzene tower and pressure swing adsorption system, described pressure swing adsorption system is made up of the adsorber of 2-6 platform parallel connection.
Wherein, described acetylene generating unit comprises carbide-feed generator, peace and quiet tower, caustic neutralizer column and condensation drying device, acetylene gas outlet is provided with bottom carbide-feed generator, described acetylene gas outlet is connected with peace and quiet tower, caustic neutralizer column, condensation drying device in turn by pipeline, and described condensation drying device connects the acetylene import of acetylene hydrogenation reaction member by pipeline.
Preferably, be provided with double-deck sieve plate in described carbide-feed generator, the spacing of the lath of upper strata sieve plate is 300mm, and the spacing of the lath of lower floor's sieve plate is 80mm.
Wherein, described paste state bed reactor is the reactor having chuck, top in reactor is provided with gas-liquid separator, reactor bottom is provided with gas distributor, dactylethrae interchanger is positioned at above gas distributor, and condenser is between gas-liquid separator and dactylethrae interchanger.
Wherein, described low temperature separation process unit comprises the flash distillation plant, deethanizing column, ethylene rectification tower, depropanizing tower, propylene rectification tower, debutanizing tower, the anti-butylene rectifying tower that connect successively.
Wherein, described CO conversion decarburization Hydrogen Unit comprises calcium carbide stove exhaust refining plant, CO changing device, decarbonization device; Described calcium carbide stove exhaust refining plant comprise be linked in sequence adsorption filter, ferric oxide desulfurizer, radial compressor, heating furnace, pre-iron molybdenum hydrogenator, one-level iron molybdenum hydrogenator, stair oxidation zinc desulfurizer, nickel Co-Mo hydrogenation reactor and secondary oxidation zinc desulfurizer.
Wherein, described decarbonization device comprises decarbonizing tower and regenerator column, described secondary oxidation zinc desulfurizer connects the bottom of described decarbonizing tower by pipeline, described decarbonizing tower top is provided with alkanolamine solution import, alkanolamine solution outlet is provided with bottom decarbonizing tower, described alkanolamine solution outlet connects regenerator column by pipeline, and the alkanolamine solution outlet of regenerator column is connected with the alkanolamine solution import of decarbonizing tower, the CO that regenerator column top is arranged
2outlet connects described carbide slag carbonation unit.
Further, acetylene gas outlet is provided with bottom described carbide-feed generator, described acetylene gas outlet is connected with peace and quiet tower, caustic neutralizer column, condensation drying device in turn by pipeline, and described condensation drying device connects the acetylene import of acetylene hydrogenation reaction member by pipeline.
Further, described pyrolysis installation is provided with fuel inlet, and the gas phase remnants outlet that described pressure-variable adsorption carries hydrogen unit is connected with the fuel inlet of described pyrolysis installation.
Adopt the system that the utility model proposes, utilize the method for fine coal preparing ethylene to comprise step:
1) pyrolysis upgrading
It is fuel rod that fine coal, unslaked lime fully mix rear extrusion molding, fuel rod is delivered to the pyrolysis installation of 800 ~ 900 DEG C, and the gas-phase product that pyrolysis produces comprises tar and pyrolysis coal gas; After pyrolysis, temperature is that the fuel rod of 600 ~ 800 DEG C is delivered in furnace of calcium carbide;
2) pressure-variable adsorption carries hydrogen
Through gas-liquid separation behind gas-phase product Quench to 60 ~ 85 DEG C that pyrolysis produces, be divided into pyrolysis coal gas and tar two-phase, pyrolysis coal gas enters transverse pipe initial cooler and cools, gas phase is cooled to 22 DEG C again, removing the tar carried secretly in gas phase through electrical tar precipitator further, obtain the pyrolysis coal gas after removing tar, removing benzene through washing benzene tower, enter pressure swing adsorption system afterwards, obtain hydrogen;
3) production calcium carbide is smelted
Fuel rod after pyrolysis is reduced at furnace of calcium carbide, is melted into calcium carbide, and deliver to carbide-feed generator after liquid calcium carbide cooling, the reaction generating tail gas in furnace of calcium carbide is:
3C+CaO→CaC
2+CO (1)
4) CO conversion, decarburization hydrogen manufacturing
Calcium carbide stove exhaust and steam preheating form hydrogen and the steam generation by reaction heat reclaimed wherein through converting after 250 DEG C, the hydrogen that conversion obtains is through entering the bottom of decarbonizing tower, with the alkanolamine solution counter current contact flowed by tower top, be then sent to the paste state bed reactor of acetylene hydrogenation reaction workshop section from top to bottom;
CO conversion produces CO
2reaction be:
CO+H
2O→CO
2+H
2(2)
5) acetylene occurs
Step 3) calcium carbide that obtains sends into carbide-feed generator and water reacts, carbide-feed generator inside is provided with double-deck sieve plate (water level is above the sieve plate of upper strata), the spacing of the lath of upper strata sieve plate is 300mm, the grand calcium carbide in 300mm and water react, the spacing of the lath of lower floor's sieve plate is 80mm, the grand calcium carbide in 80mm and water react, and are less than the calcium carbide of 80mm or powder and overflow in secondary producer secondary response again.Substantially increase the working efficiency of carbide-feed generator like this, improve calcium carbide utilization ratio.Calcium carbide produces acetylene gas after contacting with water and being hydrolyzed, and after the efficient washing cooling tower washing on secondary producer, enter positive water seal, and discharge carbide slag, acetylene hydrogenation reaction process sent into by the acetylene gas that reaction generates;
6) acetylene hydrogenation reaction
The pyrolysis coal gas of fine coal is through step 2) PSA carry hydrogen after hydrogen and calcium carbide stove exhaust convert after hydrogen and acetylene be mixed into the paste state bed reactor of acetylene hydrogenation reaction process with the ratio of 3 ~ 10:1, under the effect of catalyzer, carry out selective hydrogenation of acetylene reaction, generate the products such as ethene; It is auxiliary agent that catalyzer adopts the palladium of 20 ~ 100 μm to be main active ingredient, silver and ruthenium, aluminium sesquioxide is the catalyzer of carrier, reaction pressure is 0.2 ~ 1.5MPa, temperature of reaction is 140 ~ 220 DEG C, the condenser on slurry bed system top, by the liquid phase solvent condensation of evaporation, the liquid phase solvent of condensation is back in slurry bed system, and reaction product goes out paste state bed reactor from reactor head pneumatic outlet, enters low temperature separation process operation.
7) low temperature separation process
The product of acetylene hydrogenation is compressed to 3.4 ~ 3.9MPa, then gas phase cools and flash distillation step by step, finally be cooled to 163 ~ 169 DEG C, hydrogen is isolated in hydrogen gas tank, the liquid phase of each flash tank is entered deethanizing column, deethanizing column gaseous products enters ethylene rectification tower and obtains ethylene product, and liquid-phase product, successively through depropanizing tower, propylene rectification tower, debutanizing tower, anti-butylene rectifying tower, is separated and obtains propane, propylene, butylene, anti-butylene and C5-12 hydrocarbon.
Wherein, described fine coal is one or more in long-flame coal, bottle coal, rich coal, coking coal, meager coal, lean coal, through broken and be sized to 3 ~ 5mm, be milled to less than 150 μm afterwards, described unslaked lime is through broken and be sized to 3 ~ 5mm, regrind to the Powdered unslaked lime of less than 150 μm.Step 1) in fine coal and unslaked lime according to mass ratio (1-1.2): 1 mixes.
Step 1) in, fuel rod send in the pyrolytic process of 800 ~ 900 DEG C, and fine coal and unslaked lime, by pyrolysis processing, are stripped of the harmful elements such as part sulphur in fine coal and mercury, and can a large amount of tar of by-product and pyrolysis coal gas in pyrolytic process.Pyrolysis coal gas is carried after hydrogen through PSA and being reacted for acetylene hydrogenation, carries the fuel of the pyrolysis coal gas after hydrogen as pyrolysis installation, greatly improves the economy of integrated artistic; After pyrolysis ~ 800 DEG C of fuel rods are delivered in furnace of calcium carbide through the direct heat of conduit be connected with furnace of calcium carbide, make full use of the sensible heat of the fuel rod of pyrolysis, and improve technique overall thermal efficiency, and reduce furnace of calcium carbide power consumption.
Step 2) in, sorbing material is filled with in each adsorber, when wherein an adsorber is by pyrolysis coal gas, impurity composition in pyrolysis coal gas is obtained highly purified hydrogen by adsorbent, hydrogen purity >=99.99%, and other adsorber is in the different steps of regeneration of adsorbent beds simultaneously, each adsorber exchange-column shift, alternating sorbent and regeneration, pyrolysis coal gas is constantly inputted, and product hydrogen constantly exports.Pressure-variable adsorption puies forward the remnants of the gas phase after hydrogen as fuel for pyrolysis processing provides heat.
Step 4) the first process purification of middle calcium carbide stove exhaust, then with steam reaction, described purification comprises: calcium carbide stove exhaust enters adsorption filter after being compressed to 0.8MpaG, naphthalene, burnt oil impurities in removing calcium carbide stove exhaust, then ferric oxide desulfurizer is entered, be compressed to 3.5MPaG afterwards and enter heating furnace and pre-iron molybdenum and one-level iron molybdenum hydrogenator, enter stair oxidation zinc desulfurizer afterwards, finally enter nickel Co-Mo hydrogenation reactor and secondary oxidation zinc desulfurizer.
Step 4) in, the hydrogen that conversion obtains is through entering the bottom of decarbonizing tower, with the alkanolamine solution counter current contact flowed from top to bottom by tower top, remove acid gas composition wherein, the solution droplets that may carry in discharge knockout drum removing hydrogen, to go out in decarbonizing tower hydrogen carbon dioxide content lower than 10ppm.
Wherein, described step 4) in decarbonizing tower alkanolamine solution be MDEA, diisopropanolamine (DIPA) (DIPA), the mixture of MDEA, MEA, one or more the aqueous solution added in the mixture of alkyl alcoholamine and boratory solution of potassium carbonate or tetramethylene sulfone and diisopropanolamine (DIPA).
Further, described step 4) in decarbonizing tower after alkanolamine solution reaction, bottom decarbonizing tower, enter regenerator column regenerate, the alkanolamine solution after regeneration enters decarbonizing tower internal recycle and uses after heat exchange, cooling.
Described step 5) in reaction generate acetylene gas after wash cooling, enter peace and quiet tower 0.11% ~ 0.12% chlorine bleach liquor's cleaning showers, then caustic neutralizer column is entered, the NaOH solution of 10% ~ 14% is sprayed in caustic neutralizer column, then acetylene gas is pressurized and condensation, sends into acetylene hydrogenation reaction process.
Wherein, step 5) carbide slag that produces washes with water, and then with plate and frame(type)filter press extruding, make slag, water be separated (as water of productive use in the current Huis pond after separation), the carbide slag after separation and calcium carbide stove exhaust convert the CO produced
2reaction generates nano-calcium carbonate.
Wherein, step 5) carbide slag filters by the carbide slag that produces after washing, scalping, removing mechanical impurity, drying be sized to less than 125 μm after 1050 DEG C of calcinings, water is added after burnt carbide slag cooling, the mass ratio of water and calcium oxide is 20 ~ 40:1, obtain calcium hydroxide slurry, in aqua calcis, pass into step 4 afterwards) the rear CO produced of calcium carbide stove exhaust conversion
2carry out carbonization and obtain calcium carbonate soln, calcium carbonate soln obtains fusoid nano-calcium carbonate that particle diameter is 50 ~ 100nm after sodium laurylsulfonate surface modification, dehydration, drying.
Wherein, described step 7) in, the liquid-phase product of ethylene distillation tower bottom enters depropanizing tower, depropanizing tower gaseous products enters propylene rectification tower and obtains propylene product, liquid-phase product enters debutanizing tower, debutanizing tower gaseous products enters anti-butylene rectifying tower, and tower top obtains anti-butylene product, and liquid-phase product is the products such as the C5 of mixing.
The beneficial effects of the utility model are:
Fine coal ethylene process not only provides a kind of novel fine coal to prepare ethylene process, expanding Coal Chemical Industry Route, providing a technological line for further developing ethene downstream fine chemical product.The utility model can use cheap middle low order powdery raw coal, the high-quality resource such as block coke, blue charcoal, hard coal that fictitious hosts is high, as the carbon raw producing calcium carbide, process energy consumption is low, and in pyrolytic process, obtain tar and the pyrolysis gas by product of high added value, effectively improve technique macroeconomic; Solid product after pyrolysis adopts heat to send technique, makes full use of its sensible heat, improves technique overall thermal efficiency, and reduces furnace of calcium carbide power consumption; The hydrogen obtained after making full use of the hydrogen and calcium carbide stove exhaust conversion that pyrolysis gas product pressure-variable adsorption obtains reacts for acetylene hydrogenation, by controlling the proportioning of raw material fine coal and unslaked lime powder, ensure that the volume ratio of the acetylene that described hydrogen and calcium carbide route are produced, supply hydrogen without the need to outer completely; Another product C O after calcium carbide stove exhaust conversion
2react with the solid waste carbide slag of calcium carbide acetylene and generate nano-calcium carbonate, not only contribute to reducing environmental pollution, and can greatly increase economic efficiency.
The fine coal ethylene system that the utility model proposes, has that flow process is short, floor space is few, energy consumption is low, a less investment and reduce CO
2the advantages such as discharge, in the gaseous products of generation, ethene accounts for 75 ~ 85%, anti-butylene account for 15 ~ 20% all the other be the by product such as ethane, propylene and C5+, after reaction, gas is after low temperature separation process, and hydrogen recycle uses.
Accompanying drawing explanation
Fig. 1: the process flow sheet of fine coal ethene.
Fig. 2: the system diagram of fine coal ethene.
Embodiment
Now with following most preferred embodiment, the utility model is described, but is not used for limiting scope of the present utility model.
Embodiment 1:
See Fig. 2, a kind of system utilizing fine coal preparing ethylene, comprise pyrolysis upgrading unit, pressure-variable adsorption carries hydrogen unit, smelt and produce calcium carbide unit, CO conversion decarburization Hydrogen Unit, acetylene generating unit, acetylene hydrogenation reaction member and low temperature separation process unit;
Pyrolysis upgrading unit comprises pyrolysis installation, and described pyrolysis installation is provided with pyrolysis gas outlet, fuel inlet and discharge port, and pyrolysis gas outlet connects pressure-variable adsorption and carries hydrogen unit; Pressure-variable adsorption is carried hydrogen unit and is provided with hydrogen outlet and gas phase remnants outlet; The gas phase remnants outlet that pressure-variable adsorption carries hydrogen unit is connected with the fuel inlet of pyrolysis installation.
Smelt production calcium carbide unit and comprise furnace of calcium carbide, described furnace of calcium carbide is provided with opening for feed and offgas outlet, and the opening for feed of described furnace of calcium carbide is connected with the discharge port of described pyrolysis upgrading unit;
CO conversion decarburization Hydrogen Unit is provided with inlet mouth, hydrogen outlet and CO
2outlet, the inlet mouth of described CO conversion decarburization Hydrogen Unit is connected with the offgas outlet of described furnace of calcium carbide; The inlet mouth of described CO conversion decarburization Hydrogen Unit is also connected with steam-pipe;
Described acetylene hydrogenation reaction member comprises paste state bed reactor, described paste state bed reactor is provided with acetylene import, product gas outlet, and the hydrogen outlet that described pressure-variable adsorption carries hydrogen unit is all connected with the hydrogen outlet of described CO conversion decarburization Hydrogen Unit the hydrogen pipeline entering paste state bed reactor; The acetylene import of described paste state bed reactor connects described carbide-feed generator; Described product gas outlet connects described low temperature separation process unit; Carbide slag outlet is provided with bottom carbide-feed generator.Be provided with double-deck sieve plate in carbide-feed generator, the spacing of the lath of upper strata sieve plate is 300mm, and the spacing of the lath of lower floor's sieve plate is 80mm.
The present embodiment system also comprises carbide slag carbonation unit, and the carbide slag outlet of described carbide-feed generator connects described carbide slag carbonation unit, the CO of CO conversion decarburization Hydrogen Unit
2outlet connects carbide slag carbonation unit.
Wherein, described pressure-variable adsorption carry hydrogen unit comprise connect in turn chilling device, primary cooler, gas-liquid separator, electrical tar precipitator, wash benzene tower and pressure swing adsorption system, described pressure swing adsorption system is made up of 6 adsorbers in parallel.
In the system of the present embodiment, paste state bed reactor is the reactor having chuck, top in reactor is provided with gas-liquid separator, reactor bottom is provided with gas distributor, dactylethrae interchanger is positioned at above gas distributor, and condenser is between gas-liquid separator and dactylethrae interchanger.Low temperature separation process unit comprises the flash distillation plant, deethanizing column, ethylene rectification tower, depropanizing tower, propylene rectification tower, debutanizing tower, the anti-butylene rectifying tower that connect successively.
In the present embodiment system, CO conversion decarburization Hydrogen Unit comprises calcium carbide stove exhaust refining plant, CO changing device, decarbonization device; Described calcium carbide stove exhaust refining plant comprise be linked in sequence adsorption filter, ferric oxide desulfurizer, radial compressor, heating furnace, pre-iron molybdenum hydrogenator, one-level iron molybdenum hydrogenator, stair oxidation zinc desulfurizer, nickel Co-Mo hydrogenation reactor and secondary oxidation zinc desulfurizer.
Decarbonization device comprises decarbonizing tower and regenerator column, described secondary oxidation zinc desulfurizer connects the bottom of described decarbonizing tower by pipeline, described decarbonizing tower top is provided with alkanolamine solution import, alkanolamine solution outlet is provided with bottom decarbonizing tower, described alkanolamine solution outlet connects regenerator column by pipeline, the alkanolamine solution outlet of regenerator column is connected with the alkanolamine solution import of decarbonizing tower, the CO that regenerator column top is arranged
2outlet connects described carbide slag carbonation unit.
Be provided with acetylene gas outlet bottom carbide-feed generator, described acetylene gas outlet is connected with peace and quiet tower, caustic neutralizer column, condensation drying device in turn by pipeline, and described condensation drying device connects the acetylene import of acetylene hydrogenation reaction member by pipeline.
See Fig. 1, adopt the system of the present embodiment 1, the technique preparing ethene with fine coal is:
Fine coal is long-flame coal, through broken and be sized to 3 ~ 5mm, is milled to 20 ~ 50 μm afterwards, and unslaked lime for through broken and be sized to 3 ~ 5mm, regrind to 20 ~ 50 μm, becomes Powdered unslaked lime.Fine coal and unslaked lime mix according to mass ratio 1.06:1.
1) pyrolysis upgrading
The pelletizing of fine coal, unslaked lime fully mix rear extrusion molding to be diameter be 30mm, pelletizing is delivered to the pyrolysis installation of 900 DEG C, the gas-phase product that pyrolysis produces comprises tar and pyrolysis coal gas; After pyrolysis, temperature is that the solid product of 800 DEG C is delivered in furnace of calcium carbide; Volume ratio shared by hydrogen in pyrolysis coal gas is 42%, if do not add unslaked lime powder in same processing condition, the volume ratio shared by hydrogen in the pyrolysis coal gas that pyrolysis of coal obtains is 30%, and the interpolation of unslaked lime powder can improve the hydrogen yield of pyrolysis of coal process as can be seen here.
2) pressure-variable adsorption carries hydrogen (PSA carries hydrogen)
Through gas-liquid separation after the gas-phase product Quench to 85 DEG C that pyrolysis produces, gas phase is cooled to 22 DEG C again, the tar carried secretly in gas phase is removed further through electrical tar precipitator, obtain the pyrolysis coal gas after removing tar, benzene is removed through washing benzene tower, be with the pressure swing adsorption system that 4 adsorbers in parallel are formed afterwards, obtaining purity is the hydrogen of 99.99%; Pressure-variable adsorption puies forward the remnants of the gas phase after hydrogen as fuel for pyrolysis processing provides heat.
3) production calcium carbide is smelted
By the solid product after arc heat and resistance heat heating pyrolysis, be reduced at furnace of calcium carbide, be melted into calcium carbide, liquid calcium carbide is flowed in the pot bag of 1t by fire door, transports between building and cools, deliver to carbide-feed generator afterwards.
4) CO conversion, decarburization hydrogen manufacturing
First calcium carbide stove exhaust is compressed to after 0.8MpaG through spiral-lobe compressor and enters adsorption filter, naphthalene in removing calcium carbide stove exhaust, the impurity such as tar, remove naphthalene, the calcium carbide stove exhaust of tar etc. enters ferric oxide desulfurizer, remove most of inorganic sulfur and part organosulfur, 3.5MPaG is compressed to afterwards through radial compressor, enter heating furnace and pre-iron molybdenum and one-level iron molybdenum hydrogenator, the most of organic sulfur conversion in calcium carbide tail gas is made to be inorganic sulfur, enter stair oxidation zinc desulfurizer afterwards, remove hydrogen sulfide wherein, finally enter nickel Co-Mo hydrogenation reactor and secondary oxidation zinc desulfurizer, the total sulfur in gas is made to take off to 0.02ppm,
Calcium carbide stove exhaust hydrogen after purification mixes with the ratio of 6:1 with acetylene, be preheating to after 250 DEG C and form hydrogen and recovery steam generation by reaction heat wherein through conversion, convert the hydrogen obtained and remove through separator the bottom entering decarbonizing tower after free liquid and entrained solid impurity, with the alkanolamine solution counter current contact flowed from top to bottom by tower top, remove acid gas composition wherein, the solution droplets may carried in discharge knockout drum removing hydrogen, go out carbon dioxide content in decarbonizing tower hydrogen and, lower than 10ppm, be sent to the paste state bed reactor of acetylene hydrogenation reaction workshop section;
Alkanolamine solution is the aqueous solution of 42% of MDEA (N methyldiethanol amine).
5) acetylene occurs
Step 3) calcium carbide produced is crushed to granularity 200 ~ 400mm through calcium carbide crusher, feeding carbide-feed generator and water react, the spacing that carbide-feed generator inside is provided with the lath of double-deck sieve plate upper sieve plate is 300mm, the grand calcium carbide in 300mm and water react, the spacing of the lath of lower floor's sieve plate is 80mm, the grand calcium carbide in 80mm and water react, and are less than the calcium carbide of 80mm or powder and overflow in secondary producer secondary response again.The upper sieve plate of producer establishes umbrella to distribute cone, increases the surface-area that calcium carbide contacts with water.Calcium carbide produces acetylene gas after contacting with water and being hydrolyzed, after the efficient washing cooling tower washing on secondary producer, enter positive water seal, and discharge carbide slag, the acetylene gas that reaction generates enters peace and quiet tower and removes phosphuret-(t)ed hydrogen in acetylene gas, hydrogen sulfide and hydrogen arsenide, to go out in the acetylene gas of peace and quiet tower Phosphine content lower than 0.1ppm, hydrogen sulfide content lower than 0.1ppm and hydrogen arsenide content lower than 0.1ppm, remove phosphuret-(t)ed hydrogen, hydrogen sulfide and hydrogen arsenide and acetylene gas enter the acid mist in caustic neutralizer column removing acetylene gas, remove the acetylene gas after acid mist after supercharging and condensation, remove moisture in acetylene gas, in acetylene gas after dehydration, the content of water is 70ppm, send into acetylene hydrogenation reaction process.
The carbide slag that this step produces discharges into slag by producer and starches agitated pool, and be extracted into plate and frame(type)filter press by slush pump and extrude, slag, water are separated, and as water of productive use in the current Huis pond after separation, carbide slag and calcium carbide stove exhaust convert the CO produced
2reaction generates nano-calcium carbonate.
6) acetylene hydrogenation reaction
The pyrolysis coal gas of low order fine coal is through step 2) purification PSA carry hydrogen after hydrogen and calcium carbide stove exhaust convert after hydrogen and acetylene be mixed into the paste state bed reactor of acetylene hydrogenation reaction process with the ratio of 4 ~ 10:1, under the effect of catalyzer, carry out selective hydrogenation of acetylene reaction, generate the products such as ethene, acetylene hydrogenation catalysts adopts the palladium of 20 ~ 100 μm to be main active ingredient, silver and ruthenium are auxiliary agent, aluminium sesquioxide is the catalyzer of carrier, reaction pressure is 1.5MPa, the temperature of reaction controls at 180 DEG C, the condenser on slurry bed system top, by the liquid phase solvent condensation of evaporation, the liquid phase solvent of condensation is back in slurry bed system, the liquid phase solvent of carry secretly in reaction product 99% is separated with reaction product by the gas-liquid separator at the top of paste state bed reactor, fall back in slurry bed system, reaction product goes out paste state bed reactor from reactor head pneumatic outlet, enter low temperature separation process operation.
7) low temperature separation process
The product of acetylene hydrogenation is compressed to 3.8MPa, then gas phase cools and flash distillation step by step, finally be cooled to 163 ~ 169 DEG C, hydrogen is isolated in hydrogen gas tank, the liquid phase of each flash tank is entered deethanizing column, deethanizing column gaseous products enters ethylene rectification tower and obtains ethylene product, liquid-phase product enters depropanizing tower, depropanizing tower gaseous products enters propylene rectification tower and obtains propylene product, liquid-phase product enters debutanizing tower, debutanizing tower gaseous products enters anti-butylene rectifying tower, and tower top obtains anti-butylene product, and liquid-phase product is the hydrocarbon of more than the C5 of mixing.
8) carbide slag carbonization
Carbide slag is filtered after washing, scalping, removing mechanical impurity, drying is sized to after less than 125 μm 1050 DEG C of calcinings, water is added after burnt carbide slag cooling, the mass ratio of water and calcium oxide is 30:1, obtain calcium hydroxide slurry, the CO produced pass into calcium carbide stove exhaust conversion afterwards in aqua calcis after
2carry out carbonization and obtain calcium carbonate soln, calcium carbonate soln obtains fusoid nano-calcium carbonate that particle diameter is 50 ~ 100nm after sodium laurylsulfonate surface modification, dehydration, drying.
Those skilled in the art in the art will be appreciated that, above-described embodiment is only used to the utility model is described, and be not used as restriction of the present utility model, as long as in spirit of the present utility model, the conversion of above-described embodiment, modification all will be dropped in the scope of the utility model claim.
Claims (10)
1. one kind utilizes the system of fine coal preparing ethylene, it is characterized in that, comprise pyrolysis upgrading unit, pressure-variable adsorption carries hydrogen unit, smelt and produce calcium carbide unit, CO conversion decarburization Hydrogen Unit, acetylene generating unit, acetylene hydrogenation reaction member and low temperature separation process unit;
Described pyrolysis upgrading unit comprises pyrolysis installation, and described pyrolysis installation is provided with pyrolysis gas outlet and discharge port, and described pyrolysis gas outlet connects described pressure-variable adsorption and carries hydrogen unit;
Described pressure-variable adsorption is carried hydrogen unit and is provided with hydrogen outlet;
Described smelting is produced calcium carbide unit and is comprised furnace of calcium carbide, and described furnace of calcium carbide is provided with opening for feed and offgas outlet, and the opening for feed of described furnace of calcium carbide is connected with the discharge port of described pyrolysis upgrading unit;
CO conversion decarburization Hydrogen Unit is provided with inlet mouth, hydrogen outlet and CO
2outlet, the inlet mouth of described CO conversion decarburization Hydrogen Unit is connected with the offgas outlet of described furnace of calcium carbide; The inlet mouth of described CO conversion decarburization Hydrogen Unit is also connected with steam-pipe;
Described acetylene hydrogenation reaction member comprises paste state bed reactor, described paste state bed reactor is provided with acetylene import, product gas outlet, and the hydrogen outlet that described pressure-variable adsorption carries hydrogen unit is all connected with the hydrogen outlet of described CO conversion decarburization Hydrogen Unit the hydrogen pipeline entering paste state bed reactor; The acetylene import of described paste state bed reactor connects described acetylene generating unit; Described product gas outlet connects described low temperature separation process unit;
Described acetylene generating unit is provided with carbide slag outlet.
2. system according to claim 1, is characterized in that, also comprises carbide slag carbonation unit, and the carbide slag outlet of described acetylene generating unit connects described carbide slag carbonation unit, the CO of described CO conversion decarburization Hydrogen Unit
2outlet connects described carbide slag carbonation unit.
3. system according to claim 1, it is characterized in that, described pressure-variable adsorption carry hydrogen unit comprise connect in turn chilling device, primary cooler, gas-liquid separator, electrical tar precipitator, wash benzene tower and pressure swing adsorption system, described pressure swing adsorption system is made up of the adsorber of 2-6 platform parallel connection.
4. system according to claim 1, it is characterized in that, described acetylene generating unit comprises carbide-feed generator, peace and quiet tower, caustic neutralizer column and condensation drying device, acetylene gas outlet is provided with bottom carbide-feed generator, described acetylene gas outlet is connected with peace and quiet tower, caustic neutralizer column, condensation drying device in turn by pipeline, and described condensation drying device connects the acetylene import of acetylene hydrogenation reaction member by pipeline.
5. system according to claim 4, is characterized in that, is provided with double-deck sieve plate in described carbide-feed generator, and the spacing of the lath of upper strata sieve plate is 300mm, and the spacing of the lath of lower floor's sieve plate is 80mm.
6. system according to claim 1, is characterized in that, described pyrolysis installation is provided with fuel inlet, and the gas phase remnants outlet that described pressure-variable adsorption carries hydrogen unit is connected with the fuel inlet of described pyrolysis installation.
7. system according to claim 1, it is characterized in that, described paste state bed reactor is the reactor having chuck, top in reactor is provided with gas-liquid separator, reactor bottom is provided with gas distributor, dactylethrae interchanger is positioned at above gas distributor, and condenser is between gas-liquid separator and dactylethrae interchanger.
8. system according to claim 1, is characterized in that, described low temperature separation process unit comprises the flash distillation plant, deethanizing column, ethylene rectification tower, depropanizing tower, propylene rectification tower, debutanizing tower, the anti-butylene rectifying tower that connect successively.
9., according to the arbitrary described system of claim 1-8, it is characterized in that, described CO conversion decarburization Hydrogen Unit comprises calcium carbide stove exhaust refining plant, CO changing device, decarbonization device; Described calcium carbide stove exhaust refining plant comprise be linked in sequence adsorption filter, ferric oxide desulfurizer, radial compressor, heating furnace, pre-iron molybdenum hydrogenator, one-level iron molybdenum hydrogenator, stair oxidation zinc desulfurizer, nickel Co-Mo hydrogenation reactor and secondary oxidation zinc desulfurizer.
10. system according to claim 9, it is characterized in that, described decarbonization device comprises decarbonizing tower and regenerator column, described secondary oxidation zinc desulfurizer connects the bottom of described decarbonizing tower by pipeline, described decarbonizing tower top is provided with alkanolamine solution import, is provided with alkanolamine solution outlet bottom decarbonizing tower, and described alkanolamine solution outlet connects regenerator column by pipeline, the alkanolamine solution outlet of regenerator column is connected with the alkanolamine solution import of decarbonizing tower, the CO that regenerator column top is arranged
2outlet connects described carbide slag carbonation unit.
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| CN201520317245.7U CN204529700U (en) | 2015-05-15 | 2015-05-15 | A kind of system utilizing fine coal preparing ethylene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803819A (en) * | 2015-05-15 | 2015-07-29 | 北京神雾环境能源科技集团股份有限公司 | Method and system for producing ethylene by utilizing pulverized coal |
| CN106241735A (en) * | 2016-07-25 | 2016-12-21 | 神雾环保技术股份有限公司 | A kind of carbide slag prepares the system and method for hydrogen-rich gas and carbide |
| CN107523316A (en) * | 2017-10-17 | 2017-12-29 | 榆林煤化工产业促进中心 | A kind of hydrogen source stably decomposes complex function low temperature upgrading furnace |
| CN108299157A (en) * | 2018-01-29 | 2018-07-20 | 安徽皖维高新材料股份有限公司 | A method of preparing ethyl alcohol using calcium carbide stove exhaust |
-
2015
- 2015-05-15 CN CN201520317245.7U patent/CN204529700U/en not_active Withdrawn - After Issue
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803819A (en) * | 2015-05-15 | 2015-07-29 | 北京神雾环境能源科技集团股份有限公司 | Method and system for producing ethylene by utilizing pulverized coal |
| CN106241735A (en) * | 2016-07-25 | 2016-12-21 | 神雾环保技术股份有限公司 | A kind of carbide slag prepares the system and method for hydrogen-rich gas and carbide |
| CN107523316A (en) * | 2017-10-17 | 2017-12-29 | 榆林煤化工产业促进中心 | A kind of hydrogen source stably decomposes complex function low temperature upgrading furnace |
| CN108299157A (en) * | 2018-01-29 | 2018-07-20 | 安徽皖维高新材料股份有限公司 | A method of preparing ethyl alcohol using calcium carbide stove exhaust |
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