CN206318900U - The system that benzene is prepared by low-order coal - Google Patents
The system that benzene is prepared by low-order coal Download PDFInfo
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Abstract
The utility model discloses the system that benzene is prepared by low-order coal, including：Limestone crushing device, low-order coal breaker, the first coke oven, the second coke oven, quick lime breaker, upgraded coal breaker, press ball device, furnace of calcium carbide, calcium carbide crushing device, acetylene generator, acetylene benzene reactor and separator.Wherein, the first coke oven is connected with Limestone crushing device；Second coke oven is connected with low-order coal breaker；Quick lime breaker is connected with the first coke oven；Upgraded coal breaker is connected with the second coke oven；Press ball device is connected with quick lime breaker and upgraded coal breaker respectively；Furnace of calcium carbide has mixed material entrance, calcium carbide outlet and carbon monoxide outlet；Acetylene generator has calcium carbide particle entrance, water inlet and acetylene outlet；Benzene reactor processed has acetylene entrance, carbon dioxide entrance, carbon monoxide inlet, hydrogen inlet, methane entrance and benzene product exit.The system can realize the conversion from benzene of the coal of low value to high added value.
Description
Technical field
The utility model is related to metallurgical technology field, specifically, and the utility model is related to one kind and prepares benzene by low-order coal
System.
Background technology
The energy general layout of China is always rich coal, oil-poor, few gas, coal reserves up to world's coal reserves 17%.Its
The low-order coal such as middle lignite, jet coal resource reserve enriches, and accounts for coal in China reserves and coal production more than 50%, but due to low order
Coal water content is high, directly burns or gasification efficiency is low and prior art can not make full use of its resource value, result in coal money
The huge waste in source.In April, 2015, National Energy Board issued《Coal Clean efficiently utilizes action plan (2015-2020)》,
Coal sub-prime classified utilization status is significantly improved, the research and development and demonstration of low-order coal upgrading technology are vigorously advocated.Therefore, develop low
The clean and effective of rank coal has very great display meaning using new way.
The light aromatics such as benzene, toluene and dimethylbenzene are one of most important Elementary Chemical Industry raw material, are widely used in producing rubber
The chemical products such as glue, fiber, plastics and dyestuff.At present, aromatic hydrocarbons is mainly derived from catalytic reforming and hydro carbons heat in petrochemical industry
Solution, only about 10% derives from coal chemical industry.But petroleum resources are more and more deficienter at present, therefore, exploitation it is new by low-order coal
The technology for producing the light aromatics such as benzene is imperative.
Utility model content
The utility model is intended at least solve one of technical problem in correlation technique to a certain extent.Therefore, this reality
It is to propose a kind of system that benzene is prepared by low-order coal with a new purpose, can be realized using the system and utilize low-order coal
Maximization prepares benzene, drastically increases the yield of benzene, so as to realize turning from benzene of the low-order coal of low value to high added value
Change, and have the advantages that flow is simple, difficulty of processing is low, process costs are low and economy is high.
Of the present utility model in a first aspect, the utility model proposes the system that benzene is prepared by low-order coal, including：
Limestone crushing device, the Limestone crushing device has lime stone entrance and the outlet of lime stone particle；
Low-order coal breaker, the low-order coal breaker has low-order coal entrance and low order discharge；
First coke oven, first coke oven has lime stone particle entrance, quick lime outlet and carbon dioxide outlet, described
Lime stone particle entrance is connected with lime stone particle outlet；
Second coke oven, second coke oven has low order coal powder entrance, upgrading coal export and raw coke oven gas outlet, the low order
Coal powder entrance is connected with the low order discharge；
Quick lime breaker, the quick lime breaker has quick lime entrance and quick lime powder outlet, described
Quick lime entrance is connected with quick lime outlet；
Upgraded coal breaker, the upgraded coal breaker has upgraded coal entrance and upgraded coal dust outlet, described
Upgraded coal entrance is connected with the upgrading coal export；
Press ball device, the press ball device has quick lime powder entrance, upgraded coal powdering inlet and the outlet of material pelletizing,
The quick lime powder entrance is connected with quick lime powder outlet, the upgraded coal powdering inlet and the upgraded coal powder
Outlet is connected；
Furnace of calcium carbide, the furnace of calcium carbide has material pelletizing entrance, calcium carbide outlet and carbon monoxide outlet, the material pelletizing
Entrance is connected with material pelletizing outlet；
Calcium carbide crushing device, the calcium carbide crushing device has calcium carbide entrance and the outlet of calcium carbide particle, the calcium carbide entrance
It is connected with calcium carbide outlet；
Acetylene generator, the acetylene generator has calcium carbide particle entrance, water inlet and acetylene outlet, and the calcium carbide is broken
Material entrance is connected with calcium carbide particle outlet；
Acetylene benzene reactor, the benzene reactor processed has an acetylene entrance, carbon dioxide entrance, carbon monoxide inlet,
Hydrogen inlet, methane entrance and benzene product exit, the acetylene entrance are connected with the acetylene outlet of the acetylene generator, described
Carbon dioxide entrance is connected with the carbon dioxide outlet of first coke oven, the carbon monoxide inlet and the one of the furnace of calcium carbide
Carbon oxide outlet is connected, and hydrogen inlet and the methane entrance is connected with the raw coke oven gas outlet of second coke oven respectively；
Separator, the separator have benzene product inlet, ethene outlet and benzene outlet, the benzene product inlet with
The benzene product exit is connected.
Optionally, first coke oven and second coke oven are combustion chamber shared.
Optionally, first coke oven include it is multiple, second coke oven include multiple, the multiple first coke oven and institute
Multiple second coke ovens are stated to be alternately arranged and per shared combustion chamber between adjacent the first coke oven and the second coke oven.
Brief description of the drawings
Fig. 1 is the system structure diagram that benzene is prepared by low-order coal according to the utility model one embodiment.
Fig. 2 is that the flow for preparing benzene method using the system for preparing benzene by low-order coal of the utility model one embodiment is shown
It is intended to.
Fig. 3 is the flow that benzene method is prepared using the system for preparing benzene by low-order coal of the utility model another embodiment
Schematic diagram.
Embodiment
Embodiment of the present utility model is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning
Same or similar element or element with same or like function are represented to same or similar label eventually.Below by ginseng
The embodiment for examining accompanying drawing description is exemplary, it is intended to for explaining the utility model, and it is not intended that to the utility model
Limitation.
In one side of the present utility model, the utility model proposes a kind of system that benzene is prepared by low-order coal.According to
Embodiment of the present utility model, with reference to Fig. 1, the system includes：Limestone crushing device 100, low-order coal breaker 200,
One coke oven 300, the second coke oven 400, quick lime breaker 500, upgraded coal breaker 600, press ball device 700, furnace of calcium carbide
800th, calcium carbide crushing device 900, acetylene generator 1000, acetylene benzene reactor 1100 and separator 12000.
Wherein, lime stone breaker 100 has lime stone entrance 110 and lime stone particle outlet 120；
Low-order coal breaker 200 has low-order coal entrance 210 and low order discharge 220；
The lime stone particle entrance 310 of first coke oven 300 gives birth to ash outlet 320 and carbon dioxide outlet 330, lime stone particle entrance
310 are connected with lime stone particle outlet 120；
Second coke oven 400 has low order coal powder entrance 410, upgrading coal export 420 and raw coke oven gas outlet 430, low order coal dust
Entrance 410 is connected with low order discharge 220；
Quick lime breaker 500 have quick lime entrance 510 and quick lime powder outlet 520, quick lime entrance 510 with
Quick lime outlet 320 is connected；
Upgraded coal breaker 600 have upgraded coal entrance 610 and upgraded coal dust outlet 620, upgraded coal entrance 610 with
Upgrading coal export 420 is connected；
Press ball device 700 has quick lime powder entrance 710, upgraded coal powdering inlet 720 and material pelletizing outlet 730,
Quick lime powder entrance 710 is connected with quick lime powder outlet 520, upgraded coal powdering inlet 720 and upgraded coal dust outlet 620
It is connected；
Furnace of calcium carbide 800 has material pelletizing entrance 810, calcium carbide outlet 820 and carbon monoxide outlet 830, and material pelletizing enters
Mouth 810 is connected with material pelletizing outlet 730；
Calcium carbide crushing device 900 has calcium carbide entrance 910 and calcium carbide particle outlet 920, and calcium carbide entrance 910 is exported with calcium carbide
820 are connected；
Acetylene generator 1000 has calcium carbide particle entrance 1010, water inlet 1020 and acetylene outlet 1030, calcium carbide particle
Entrance 1010 connects with calcium carbide particle outlet phase 920；
Benzene reactor 1100 processed has acetylene entrance 1110, carbon dioxide entrance 1120, carbon monoxide inlet 1130, hydrogen
Entrance 1140, methane entrance 1150 and benzene product exit 1160, the acetylene of acetylene entrance 1110 and acetylene generator 1000 are exported
1030 are connected, and carbon dioxide entrance 1120 is connected with the carbon dioxide outlet 330 of the first coke oven 300, carbon monoxide inlet 1130
Be connected with the carbon monoxide of furnace of calcium carbide 800 outlet 830, hydrogen inlet 1140 and methane entrance 1150 respectively with the second coke oven 400
Raw coke oven gas outlet 430 be connected；
Separator 1200 has benzene product inlet 1210, ethene outlet 1220 and benzene outlet 1230, benzene product inlet
1210 are connected with benzene product exit 1160.
Thus, using the system that benzene is prepared by low-order coal of the utility model embodiment, first by coal aromatic hydrocarbons, solve
The problem of aromatic production brought because petroleum resources are limited is limited, realizes from the low-order coal of low value to the virtue of high added value
The transition process of hydrocarbon；Secondly, by low-order coal upgrading, gaseous product is used as fuel gas and acetylene benzene reactor feed gas；Upgraded coal
Calcium carbide is produced with quick lime, acetylene is prepared, as the unstripped gas of acetylene benzene reactor, the clean and effective profit of low-order coal is realized
With；In addition, combustion chamber shared, the combustible gas offer that chamber fuel is produced by coal upgrading richness, coke oven are fired in coal upgrading with lime stone
The hot material heat of mixing of production feed into furnace of calcium carbide, effectively reduces the energy consumption of technique.Therefore, using the utility model embodiment
The system that benzene is prepared by low-order coal can realize and prepare benzene using fine coal maximization, drastically increase the yield of benzene so that
The conversion from benzene of the coal of low value to high added value is realized, and with flow is simple, difficulty of processing is low, process costs are low and warp
The high advantage of Ji property.
The system that benzene is prepared by fine coal of the utility model specific embodiment is described in detail below with reference to Fig. 1.
Limestone crushing device 100
According to embodiment of the present utility model, there is lime stone breaker 100 lime stone entrance 110 and lime stone particle to go out
Mouth 120.Thus, lime stone is subjected to break process, to obtain lime stone particle.
According to embodiment of the present utility model, lime stone is that calcium carbonate content is higher (typically more than 97%), impurity compared with
Few lime stone.Inventor has found, by the way that lime stone and low-order coal are carried out into pulverization process respectively, can increase the table of lime stone
Area, and low-order coal can be made to be sufficiently mixed with the unclassified stores in subsequent step, so as to improve reaction efficiency and yield.
According to embodiment of the present utility model, the average grain diameter of lime stone particle can be not higher than 45mm, preferably 5-45mm.
Inventor has found, in follow-up firing processing, if the particle diameter of lime stone particle is excessive, can not be fully converted into quick lime, and
Required energy consumption can be made higher；And if agstone is broken into smaller particle, then can significantly improve the cost of pulverization process.Invention
People is had found by many experiments, and agstone is broken into the lime stone particle that average grain diameter is 5-45mm, can ensure to crush
While processing cost is relatively low, make lime stone particle prepare quick lime reaction efficiency, energy consumption and yield it is optimal.
Low-order coal breaker 200
According to embodiment of the present utility model, there is low-order coal breaker 200 low-order coal entrance 210 and low order coal dust to go out
Mouth 220.Thus, low-order coal is subjected to break process, to obtain low order coal dust.
According to embodiment of the present utility model, low-order coal is the low-quality coal that volatile matter is more than 35wt%.Volatile matter is pyrolyzed
The raw coke oven gas purification of gained can obtain the combustible components such as hydrogen, methane, carbon monoxide, light hydrocarbons, and wherein methane and hydrogen can
As the raw material of acetylene benzene reactor in step S600, the part that furnace of calcium carbide is obtained in remaining fuel gas and step S400
Carbon monoxide can be the thermal source of the combustion chamber of coke oven in step S200 and step S300, realize effective utilization of resource.
According to embodiment of the present utility model, the average grain diameter of low order coal dust can be not higher than 25mm, preferably 5-25mm.Hair
If a person of good sense it was unexpectedly observed that the average grain diameter of low order coal dust is excessive, can not be sufficiently mixed by many experiments with lime stone,
It so as to reduce the efficiency of follow-up calcium carbide reaction, and can raise required energy consumption；And if low-order coal is crushed into smaller particle, then
The cost of pulverization process can be significantly improved.Inventor is had found by many experiments, and low-order coal is ground into average grain diameter for 5-
25mm low order coal dust, can ensure that pulverization process is lower-cost simultaneously, make efficiency, energy consumption and the production of follow-up calcium carbide reaction
Rate is optimal.
First coke oven 300
According to embodiment of the present utility model, the lime stone particle entrance 310 of the first coke oven 300 gives birth to ash outlet 320 and titanium dioxide
Carbon outlet 330, lime stone particle entrance 310 is connected with lime stone particle outlet 120.Thus, lime stone particle is supplied to
Processing is fired in one coke oven 300, to obtain quick lime and carbon dioxide.Can be effective from there through the first coke oven 300
Ground is fired processing to lime stone particle, and obtains quick lime and carbon dioxide.
Second coke oven 400
According to embodiment of the present utility model, the second coke oven 400 has low order coal powder entrance 410, the and of upgrading coal export 420
Raw coke oven gas outlet 430, low order coal powder entrance 410 is connected with low order discharge 220.Thus, low order coal dust is supplied to second
Upgrading processing is carried out in coke oven 400, to obtain upgraded coal and raw coke oven gas.
According to embodiment of the present utility model, the first coke oven and the second coke oven are combustion chamber shared.It is possible thereby to effectively reduction
Energy consumption.According to specific embodiment of the utility model, the first coke oven 300 can include multiple, and the second coke oven 400 can also include
Multiple, multiple first coke ovens 300 are alternately arranged with multiple second coke ovens 400 and per adjacent the first coke oven 300 and the second coke oven
Combustion chamber is shared between 400.It is possible thereby to share heat to greatest extent, energy consumption is preferably minimized.
According to embodiment of the present utility model, the firing carried out in the first coke oven 300 is handled to be carried out with the second coke oven 400
Upgrading handle under 1000 degrees Celsius carry out 12 hours and complete jointly.It is possible thereby to effectively while completing
Lime stone particle fires the upgrading with low order coal dust, and then obtains quick lime and upgraded coal, and produces carbon dioxide and substantial amounts of
Raw coke oven gas.Carbon dioxide and substantial amounts of raw coke oven gas can be recycled the step of subsequently benzene is prepared, and then improve resource
Utilization rate and reduction prepare the cost of benzene.
Quick lime breaker 500
Quick lime breaker 500 have quick lime entrance 510 and quick lime powder outlet 520, quick lime entrance 510 with
Quick lime outlet 320 is connected.Quick lime is subjected to break process, to obtain quick lime powder.
According to embodiment of the present utility model, the average grain diameter of quick lime powder is respectively less than 20 microns.Quick lime and it will carry
Matter coal dust is broken into after powder and mixed, and can be effectively increased the contact area of reactant, the reaction efficiency of furnace of calcium carbide is improved, so as to reduce
The energy consumption of reaction of furnace of calcium carbide, increases treating capacity.
Upgraded coal breaker 600
Upgraded coal breaker 600 have upgraded coal entrance 610 and upgraded coal dust outlet 620, upgraded coal entrance 610 with
Upgrading coal export 420 is connected.Upgraded coal is subjected to break process, to obtain upgraded coal powder.
According to embodiment of the present utility model, the average grain diameter of upgraded coal powder is respectively less than 20 microns.Quick lime and it will carry
Matter coal dust is broken into after powder and mixed, and can be effectively increased the contact area of reactant, the reaction efficiency of furnace of calcium carbide is improved, so as to reduce
The energy consumption of reaction of furnace of calcium carbide, increases treating capacity.
Press ball device 700
Press ball device 700 has quick lime powder entrance 710, upgraded coal powdering inlet 720 and material pelletizing outlet 730,
Quick lime powder entrance 710 is connected with quick lime powder outlet 520, upgraded coal powdering inlet 720 and upgraded coal dust outlet 620
It is connected.Thus, upgraded coal powder and quick lime powder are subjected to mixing and pressure ball is handled, to obtain material pelletizing.
According to embodiment of the present utility model, the mass ratio 1 of upgraded coal and quick lime：(1-2).When coal dust proportioning is too high,
Carbon residue is higher in calcium carbide furnace discharge, and quick lime is superfluous when too low, and influence produces electricity stone quality.
According to embodiment of the present utility model, the average grain diameter of material pelletizing is 10-40mm.The size controlling of pelletizing is existed
Be conducive to heat transfer in above range, improve the thermal efficiency.
Furnace of calcium carbide 800
According to embodiment of the present utility model, furnace of calcium carbide 800 has material pelletizing entrance 810, calcium carbide outlet 820 and an oxygen
Change carbon outlet 830, material pelletizing entrance 810 is connected with material pelletizing outlet 730.Upgraded coal and quicklime mixture material are heat-fed
Calcium carbide reaction is carried out in furnace of calcium carbide, to obtain calcium carbide and carbon monoxide.Carbon monoxide can be former as follow-up benzene reaction processed
Material, and then improve resource utilization.
Calcium carbide crushing device 900
According to embodiment of the present utility model, there is calcium carbide crushing device 900 calcium carbide entrance 910 and calcium carbide particle to export
920, calcium carbide entrance 910 is connected with calcium carbide outlet 820.It is possible thereby to which calcium carbide is crushed into appropriate particle size.
According to embodiment of the present utility model, calcium carbide can be crushed to particle diameter not higher than 80mm, preferably calcium carbide is crushed
It is 50~80mm to particle diameter.Inventor has found, if the particle diameter of calcium carbide is excessive, can not fully be reacted with water and prepare second
Alkynes, and can raise required energy consumption；And if calcium carbide is crushed into smaller particle, then can significantly improve the cost of break process.
Inventor is had found by many experiments, and calcium carbide is crushed into particle diameter for 50~80mm, can ensure that break process cost is relatively low
While, make to prepare the reaction efficiency of acetylene, energy consumption and yield optimal.
Acetylene generator 1000
According to embodiment of the present utility model, acetylene generator 1000 has calcium carbide particle entrance 1010, water inlet 1020
With acetylene outlet 1030, calcium carbide particle entrance 1010 connects with calcium carbide particle outlet phase 920.Thus, by calcium carbide after crushing in second
Reacted in alkynes generator 1000 with water, to obtain acetylene.
Acetylene benzene reactor 1100
According to embodiment of the present utility model, benzene reactor 1100 processed has acetylene entrance 1110, carbon dioxide entrance
1120th, carbon monoxide inlet 1130, hydrogen inlet 1140, methane entrance 1150 and benzene product exit 1160, acetylene entrance 1110
It is connected with the acetylene outlet 1030 of acetylene generator 1000, the carbon dioxide of carbon dioxide entrance 1120 and the first coke oven 300 goes out
Mouth 330 is connected, and carbon monoxide inlet 1130 is connected with the carbon monoxide outlet 830 of furnace of calcium carbide 800, hydrogen inlet 1140 and methane
Entrance 1150 is connected with the raw coke oven gas outlet 430 of the second coke oven 400 respectively.
Thus, produced in the hydrogen and methane, the first coke oven 300 in the raw coke oven gas that will be produced in acetylene, the second coke oven 400
Carbon dioxide and furnace of calcium carbide 800 in produce carbon monoxide be passed through in acetylene benzene reactor and react, to obtain
Obtain benzo by-product ethene.
It will be appreciated to those of skill in the art that acetylene benzene reactor is by heating furnace and at least one quartz ampoule group
Into, and there is flat-temperature zone in heating furnace, above-mentioned mixed gas enters heating furnace flat-temperature zone by quartzy tube inlet, is obtained by reaction
Benzo by-product ethene, obtained benzene and ethene is exported from quartz ampoule to flow out.
According to embodiment of the present utility model, quartzy bore is 1 with flat-temperature zone length ratio：(50~100).Inventor
It was found that, the thermal field inside the ratio regular meeting influence reaction tube of quartzy bore and constant temperature section length, so as to change the conversion ratio of reaction
And selectivity.
According to embodiment of the present utility model, the temperature of quartz ampoule entrance and exit can be not higher than 200 degrees Celsius.Invention
People has found, when the temperature in metal tubes is more than 200 degrees Celsius, and the metal in pipeline can a large amount of hydrogen of catalytic reaction gas generation
And carbon monoxide, the yield of other products such as benzene and ethene is almost reduced to 0.
According to embodiment of the present utility model, above-mentioned reaction can be carried out under 600~1000 degrees Celsius.Invention human hair
Existing, when reaction temperature is too low, conversion of alkyne is substantially reduced；When reaction temperature is too high, the reaction aggravation of ethene hot polymerization is reduced
The yield of the lighter products such as benzene simultaneously adds coke yield.
According to preferred embodiment of the present utility model, above-mentioned reaction can be carried out under 850~950 degrees Celsius.Inventor
It was found that, reacted at such a temperature, the efficiency, energy consumption and yield of reaction can be made optimal.
According to one embodiment of the present utility model, acetylene in reaction, hydrogen, methane, carbon dioxide and carbon monoxide
Mixed proportion is not particularly restricted, and those skilled in the art can be selected according to actual needs, according to the utility model
Specific embodiment, acetylene in reaction, hydrogen, methane, the volume ratio of carbon dioxide and carbon monoxide can be (1~2)：(1~
4)：(1~2)：(1~3)：(0.5~1).Inventor is by many experiments it was unexpectedly observed that the change of acetylene ratio can influence second
The yield of alkyne conversion rate and coke；Hydrogen ratio, which changes, can influence the yield of the hydrogenation products such as coke and ethene, ethane；Methane
Coke yield can be influenceed by changing with carbon monoxide ratio；Carbon dioxide ratio, which changes, can influence the partial pressure of reaction gas, so as to influence
Reaction depth.Acetylene yield can be further improved from there through using said ratio.
Separator 1200
According to embodiment of the present utility model, there is separator 1200 benzene product inlet 1210, ethene to export 1220 and
Benzene outlet 1230, benzene product inlet 1210 is connected with benzene product exit 1160.Separator 1200 is suitable to react acetylene benzene
The benzene and the ethylene separation of by-product obtained in device 1100.
Thus, passed through according to the system for preparing benzene by low-order coal of the utility model embodiment respectively by lime stone and low order
Coal carries out pulverization process and obtains lime stone particle and low order coal dust, and by lime stone particle and low order coal dust combustion chamber shared
It is fired in coke oven and upgrading, reduces energy consumption.The mixed material for obtaining upgraded coal and quick lime obtains calcium carbide through calcium carbide reaction
And carbon monoxide, further calcium carbide and water are reacted, acetylene is obtained, finally by acetylene and hydrogen, methane, above reaction produce
Carbon dioxide and carbon monoxide mixing are passed through acetylene benzene reactor and reacted, to obtain target product benzo by-product second
Alkene, and then separated the two by separator.Profit can be realized using the system of the present utility model for preparing benzene by low-order coal
Benzene is prepared with low-order coal maximization, the yield of benzene is drastically increased, so as to realize from the low-order coal of low value to high added value
Benzene conversion, and have the advantages that flow is simple, difficulty of processing is low, process costs are low and economy is high.
The system that benzene is prepared by coal of the utility model above-described embodiment is understood for convenience, below with reference to Fig. 2-3 pairs of profits
The method for preparing benzene with the system is described.
Included according to the method for preparing benzene by low-order coal of the utility model embodiment：(1) by lime stone and low-order coal point
Break process is not carried out, to obtain lime stone particle and coal dust；(2) lime stone particle is supplied and place is fired to coke oven
Reason, to obtain quick lime and carbon dioxide；(3) coal dust is supplied to coke oven and carries out upgrading processing, to obtain upgraded coal
And raw coke oven gas；(4) quick lime and upgraded coal are subjected to break process respectively, to obtain quick lime powder and upgraded coal powder；
(5) upgraded coal powder and quick lime powder are subjected to mixing and pressure ball is handled, to obtain material pelletizing；(6) by material pelletizing
Calcium carbide reaction is carried out in supply to furnace of calcium carbide, to obtain calcium carbide and carbon monoxide；(7) calcium carbide is occurred in acetylene after crushing
Reacted in device with water, to obtain acetylene；And (8) by acetylene, step (3) produce raw coke oven gas in hydrogen and methane, step
Suddenly the carbon monoxide that the carbon dioxide and step (6) that (2) are produced are produced is passed through in acetylene benzene reactor and reacted, with
Just benzo by-product ethene is obtained.
Thus using the method that benzene is prepared by low-order coal of the utility model embodiment, first by coal aromatic hydrocarbons, solve
The problem of aromatic production brought because petroleum resources are limited is limited, realizes from the low-order coal of low value to the virtue of high added value
The transition process of hydrocarbon.Secondly, by low-order coal upgrading, gaseous product is used as fuel gas and acetylene benzene reactor feed gas；Upgraded coal
Calcium carbide is produced with quick lime, acetylene is prepared, as the unstripped gas of acetylene benzene reactor, the clean and effective profit of low-order coal is realized
With.Therefore, it can realize to maximize using low-order coal using the system for preparing benzene by low-order coal of the utility model embodiment and make
Standby benzene, drastically increases the yield of benzene, so that the conversion from benzene of the coal of low value to high added value is realized, and with flow
Simply, the advantage that difficulty of processing is low, process costs are low and economy is high.
The method that benzene is prepared by low-order coal of the utility model specific embodiment is described in detail below with reference to Fig. 2-3.
S100：The break process of lime stone and low-order coal
According to embodiment of the present utility model, lime stone and low-order coal are subjected to break process respectively, to obtain lime
Stone particle and low order coal dust.
According to embodiment of the present utility model, lime stone and low-order coal are subjected to break process respectively, to obtain lime
Stone particle and coal dust.
According to embodiment of the present utility model, lime stone is that calcium carbonate content is higher (typically more than 97%), impurity compared with
Few lime stone.Inventor has found, by the way that lime stone and low-order coal are carried out into pulverization process respectively, can increase the table of lime stone
Area, and low-order coal can be made to be sufficiently mixed with the unclassified stores in subsequent step, so as to improve reaction efficiency and yield.
According to embodiment of the present utility model, the average grain diameter of lime stone particle can be not higher than 45mm, preferably 5-45mm.
Inventor has found, in follow-up firing processing, if the particle diameter of lime stone particle is excessive, can not be fully converted into quick lime, and
Required energy consumption can be made higher；And if agstone is broken into smaller particle, then can significantly improve the cost of pulverization process.Invention
People is had found by many experiments, and agstone is broken into the lime stone particle that average grain diameter is 5-45mm, can ensure to crush
While processing cost is relatively low, make lime stone particle prepare quick lime reaction efficiency, energy consumption and yield it is optimal.
According to embodiment of the present utility model, low-order coal is the low-quality coal that volatile matter is more than 35wt%.Volatile matter is pyrolyzed
The raw coke oven gas purification of gained can obtain the combustible components such as hydrogen, methane, carbon monoxide, light hydrocarbons, and wherein methane and hydrogen can
As the raw material of acetylene benzene reactor in step S600, the part that furnace of calcium carbide is obtained in remaining fuel gas and step S400
Carbon monoxide can be the thermal source of the combustion chamber of coke oven in step S200 and step S300, realize effective utilization of resource.
According to embodiment of the present utility model, the average grain diameter of low order coal dust can be not higher than 25mm, preferably 5-25mm.Hair
If a person of good sense it was unexpectedly observed that the average grain diameter of low order coal dust is excessive, can not be sufficiently mixed by many experiments with lime stone,
It so as to reduce the efficiency of follow-up calcium carbide reaction, and can raise required energy consumption；And if low-order coal is crushed into smaller particle, then
The cost of pulverization process can be significantly improved.Inventor is had found by many experiments, and low-order coal is ground into average grain diameter for 5-
25mm low order coal dust, can ensure that pulverization process is lower-cost simultaneously, make efficiency, energy consumption and the production of follow-up calcium carbide reaction
Rate is optimal.
S200：Lime calcining stone particle in coke oven
According to embodiment of the present utility model, lime stone particle is supplied processing is fired to coke oven, to obtain
Quick lime and carbon dioxide.Processing effectively can be fired to lime stone particle from there through coke oven, and obtain quick lime
And carbon dioxide.
S300：Upgrading low order coal dust in coke oven
According to embodiment of the present utility model, low order coal dust is supplied to coke oven and carries out upgrading processing, to be carried
Matter coal and raw coke oven gas.
According to embodiment of the present utility model, the coke oven used in step S200 is shared with the coke oven used in step S300
Combustion chamber.It is possible thereby to effectively reduce energy consumption.According to embodiment of the present utility model, firing processing and step in step S200
S300 upgrading, which is handled, to be carried out 12 hours and completes jointly under 1000 degrees Celsius.It is possible thereby to effectively while
The firing of lime stone particle and the upgrading of low order coal dust are completed, and then obtains quick lime and upgraded coal, and produces carbon dioxide and big
The raw coke oven gas of amount.Carbon dioxide and substantial amounts of raw coke oven gas can be recycled the step of subsequently benzene is prepared, and then be improved
Resource utilization and reduction prepare the cost of benzene.
S400：The break process of quick lime and upgraded coal
According to embodiment of the present utility model, quick lime and upgraded coal are subjected to break process respectively, to obtain giving birth to stone
Grey powder and upgraded coal powder.
According to embodiment of the present utility model, the average grain diameter of quick lime powder and upgraded coal powder is respectively less than 20 microns.
Quick lime and upgraded coal are ground into after powder and mixed, the contact area of reactant can be effectively increased, the reaction of furnace of calcium carbide is improved
Efficiency, so as to reduce the energy consumption of reaction of furnace of calcium carbide, increases treating capacity.
S500:Mixing and pressure ball processing
According to embodiment of the present utility model, upgraded coal powder and quick lime powder are subjected to mixing and pressure ball is handled, with
Just material pelletizing is obtained.
According to embodiment of the present utility model, in the step, the mass ratio 1 of upgraded coal and quick lime：(1-2).Coal dust is matched somebody with somebody
Than it is too high when, carbon residue is higher in calcium carbide furnace discharge, and quick lime is superfluous when too low, and influence produces electricity stone quality.
According to embodiment of the present utility model, the average grain diameter of material pelletizing is 10-40mm.The size controlling of pelletizing is existed
Be conducive to heat transfer in above range, improve the thermal efficiency.
600：Prepare calcium carbide
According to embodiment of the present utility model, progress calcium carbide is heat-fed to furnace of calcium carbide after upgraded coal and quick lime are mixed anti-
Should, to obtain calcium carbide and carbon monoxide.
S700：Calcium carbide prepares acetylene
According to embodiment of the present utility model, calcium carbide is reacted in acetylene generator with water after crushing, to obtain
Acetylene.
According to embodiment of the present utility model, in the step, calcium carbide can be crushed to particle diameter not higher than 80mm, preferably will
Calcium carbide is crushed to particle diameter for 50~80mm.Inventor is had found, if the particle diameter of calcium carbide is excessive, preparation can not be fully reacted with water
Acetylene is obtained, and can raise required energy consumption；And if calcium carbide is crushed into smaller particle, then can significantly improve break process
Cost.Inventor is had found by many experiments, and calcium carbide is crushed into particle diameter for 50~80mm, can ensure break process cost
While relatively low, make to prepare the reaction efficiency of acetylene, energy consumption and yield optimal.
S800：Acetylene prepares benzene
According to embodiment of the present utility model, hydrogen and methane, step in the raw coke oven gas that acetylene, step S300 are produced
The carbon monoxide that the carbon dioxide and step S400 that S200 is produced are produced is passed through in acetylene benzene reactor and reacted, with
Just benzo by-product ethene is obtained.
It will be appreciated to those of skill in the art that acetylene benzene reactor is by heating furnace and at least one quartz ampoule group
Into, and there is flat-temperature zone in heating furnace, above-mentioned mixed gas enters heating furnace flat-temperature zone by quartzy tube inlet, is obtained by reaction
Benzo by-product ethene, obtained benzene and ethene is exported from quartz ampoule to flow out.
According to embodiment of the present utility model, quartzy bore is 1 with flat-temperature zone length ratio：(50~100).Inventor
It was found that, the thermal field inside the ratio regular meeting influence reaction tube of quartzy bore and constant temperature section length, so as to change the conversion ratio of reaction
And selectivity.
According to embodiment of the present utility model, the temperature of quartz ampoule entrance and exit can be not higher than 200 degrees Celsius.Invention
People has found, when the temperature in metal tubes is more than 200 degrees Celsius, and the metal in pipeline can a large amount of hydrogen of catalytic reaction gas generation
And carbon monoxide, the yield of other products such as benzene and ethene is almost reduced to 0.
According to embodiment of the present utility model, above-mentioned reaction can be carried out under 600~1000 degrees Celsius.Invention human hair
Existing, when reaction temperature is too low, conversion of alkyne is substantially reduced；When reaction temperature is too high, the reaction aggravation of ethene hot polymerization is reduced
The yield of the lighter products such as benzene simultaneously adds coke yield.
According to preferred embodiment of the present utility model, above-mentioned reaction can be carried out under 850~950 degrees Celsius.Inventor
It was found that, reacted at such a temperature, the efficiency, energy consumption and yield of reaction can be made optimal.
According to one embodiment of the present utility model, acetylene in reaction, hydrogen, methane, carbon dioxide and carbon monoxide
Mixed proportion is not particularly restricted, and those skilled in the art can be selected according to actual needs, according to the utility model
Specific embodiment, acetylene in reaction, hydrogen, methane, the volume ratio of carbon dioxide and carbon monoxide can be (1~2)：(1~
4)：(1~2)：(1~3)：(0.5~1).Inventor is by many experiments it was unexpectedly observed that the change of acetylene ratio can influence second
The yield of alkyne conversion rate and coke；Hydrogen ratio, which changes, can influence the yield of the hydrogenation products such as coke and ethene, ethane；Methane
Coke yield can be influenceed by changing with carbon monoxide ratio；Carbon dioxide ratio, which changes, can influence the partial pressure of reaction gas, so as to influence
Reaction depth.Acetylene yield can be further improved from there through using said ratio.
Following advantages are at least had according to the method for preparing benzene by low-order coal of the utility model above-described embodiment：
(1) by coal aromatic hydrocarbons, solve the problem of aromatic production brought because petroleum resources are limited is limited, realize from
Transition process of the low-order coal of low value to the aromatic hydrocarbons of high added value.
(2) by low-order coal upgrading, gaseous product is used as fuel gas and acetylene benzene reactor feed gas；Upgraded coal and quick lime
Calcium carbide is produced, acetylene is prepared, as the unstripped gas of acetylene benzene reactor, the clean and effective for realizing low-order coal is utilized.
(3) combustion chamber shared, the combustible gas offer that chamber fuel is produced by coal upgrading richness is fired in coal upgrading with lime stone, burnt
The hot material heat of mixing of stove production feed into furnace of calcium carbide, effectively reduces the energy consumption of technique.
(4) semicoke and quick lime are pulverized and mixed rear pressure ball, enter back into furnace of calcium carbide, significantly improve connecing for coal and quick lime
Contacting surface is accumulated, and improves reaction efficiency, reduces system energy consumption.
Below with reference to specific embodiment, the utility model is described, it is necessary to which explanation is, these embodiments are only
Descriptive, without limiting the utility model in any way.
Embodiment 1
Agstone is broken to below 45mm, from 5~45mm particle diameters, fired through belt-conveying to coke oven.By middle low order
Coal dust is broken to below 25mm, from 5~25mm particle diameters, is pyrolyzed through belt-conveying to coke oven.Middle low-order coal and lime stone mass ratio
For 1:2, coke oven combustion chamber heating-up temperature is 1000 DEG C.After 12h is fired and is pyrolyzed, upgraded coal is broken to particle diameter with calcium lime powder
Less than 20 μm, mixed material is molded into press ball device, and the pelletizing after shaping loads the elevated bunker of system for producing calcium carbide
In, it is reloaded into furnace of calcium carbide production calcium carbide.The calcium carbide cooling crush produced, by the size controlling of calcium carbide between 50~80mm,
Reaction obtains acetylene into acetylene generator.By the system, low-order coal can obtain with 2000kg lime stones in 1000kg
355kg or so acetylene, 88kg or so hydrogen, 234kg or so methane, 800kg carbon dioxide and 403kg carbon monoxide.
Acetylene, hydrogen, methane, carbon dioxide and the 191kg carbon monoxide of gained, which are passed through in acetylene benzene reactor, to be reacted, and is mixed
The reaction time for closing gas is 10s, and reaction temperature is 900 DEG C, and reactor uses the pipe being made up of internal diameter for 4mm quartz ampoule
Beam, reactor flat-temperature zone is 300mm.Production obtains 166kg benzene and 92kg ethene.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present utility model or example.In this manual, to the schematic table of above-mentioned term
Identical embodiment or example need not be directed to by stating.Moreover, specific features, structure, material or the feature of description can be
Combined in an appropriate manner in any one or more embodiments or example.In addition, in the case of not conflicting, this area
Technical staff can be carried out the feature of the not be the same as Example described in this specification or example and non-be the same as Example or example
With reference to and combination.
Although embodiment of the present utility model has been shown and described above, it is to be understood that above-described embodiment is
Exemplary, it is impossible to it is interpreted as to limitation of the present utility model, one of ordinary skill in the art is in scope of the present utility model
It is interior above-described embodiment to be changed, changed, replaced and modification.
Claims (3)
1. a kind of system that benzene is prepared by low-order coal, it is characterised in that including：
Limestone crushing device, the Limestone crushing device has lime stone entrance and the outlet of lime stone particle；
Low-order coal breaker, the low-order coal breaker has low-order coal entrance and low order discharge；
First coke oven, first coke oven has lime stone particle entrance, quick lime outlet and carbon dioxide outlet, the lime
Stone particle entrance is connected with lime stone particle outlet；
Second coke oven, second coke oven has low order coal powder entrance, upgrading coal export and raw coke oven gas outlet, the low order coal dust
Entrance is connected with the low order discharge；
Quick lime breaker, the quick lime breaker has quick lime entrance and quick lime powder outlet, the raw stone
Grey entrance is connected with quick lime outlet；
Upgraded coal breaker, the upgraded coal breaker has upgraded coal entrance and upgraded coal dust outlet, the upgrading
Coal entrance is connected with the upgrading coal export；
Press ball device, the press ball device has quick lime powder entrance, upgraded coal powdering inlet and the outlet of material pelletizing, described
Quick lime powder entrance is connected with quick lime powder outlet, the upgraded coal powdering inlet and the upgraded coal dust outlet
It is connected；
Furnace of calcium carbide, the furnace of calcium carbide has material pelletizing entrance, calcium carbide outlet and carbon monoxide outlet, the material pelletizing entrance
It is connected with material pelletizing outlet；
Calcium carbide crushing device, the calcium carbide crushing device has calcium carbide entrance and the outlet of calcium carbide particle, the calcium carbide entrance and institute
Calcium carbide outlet is stated to be connected；
Acetylene generator, the acetylene generator has calcium carbide particle entrance, water inlet and acetylene outlet, and the calcium carbide particle enters
Mouth is connected with calcium carbide particle outlet；
Acetylene benzene reactor, the benzene reactor processed has acetylene entrance, carbon dioxide entrance, carbon monoxide inlet, hydrogen
Entrance, methane entrance and benzene product exit, the acetylene entrance are connected with the acetylene outlet of the acetylene generator, the dioxy
Change carbon entrance with the carbon dioxide outlet of first coke oven to be connected, an oxidation of the carbon monoxide inlet and the furnace of calcium carbide
Carbon outlet is connected, and hydrogen inlet and the methane entrance is connected with the raw coke oven gas outlet of second coke oven respectively；
Separator, the separator have benzene product inlet, ethene outlet and benzene outlet, the benzene product inlet with it is described
Benzene product exit is connected.
2. the system of benzene is prepared by low-order coal according to claim 1, it is characterised in that first coke oven and described second
Coke oven is combustion chamber shared.
3. the system of benzene is prepared by low-order coal according to claim 1, it is characterised in that first coke oven include it is multiple,
Second coke oven includes multiple, and the multiple first coke oven and the multiple second coke oven are alternately arranged and per adjacent first
Combustion chamber is shared between coke oven and the second coke oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621363355.8U CN206318900U (en) | 2016-12-12 | 2016-12-12 | The system that benzene is prepared by low-order coal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621363355.8U CN206318900U (en) | 2016-12-12 | 2016-12-12 | The system that benzene is prepared by low-order coal |
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| Publication Number | Publication Date |
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| CN206318900U true CN206318900U (en) | 2017-07-11 |
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| CN201621363355.8U Expired - Fee Related CN206318900U (en) | 2016-12-12 | 2016-12-12 | The system that benzene is prepared by low-order coal |
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| Country | Link |
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2016
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