CN206318896U - 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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- CN206318896U CN206318896U CN201621361136.6U CN201621361136U CN206318896U CN 206318896 U CN206318896 U CN 206318896U CN 201621361136 U CN201621361136 U CN 201621361136U CN 206318896 U CN206318896 U CN 206318896U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The utility model discloses the system that benzene is prepared by low-order coal, including：Low-order coal breaker, limekiln, quick lime breaker, press ball device, revolving bed pyrolysis installation, furnace of calcium carbide, calcium carbide crushing device, acetylene generator, acetylene benzene reactor and separator.Wherein, press ball device has low-order coal powdering inlet, quick lime powder entrance and the outlet of material pelletizing；Revolving bed pyrolysis installation has material pelletizing entrance, the outlet of pyrolysis pelletizing, coal tar oil export and pyrolysis gas outlet；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, and the calcium carbide particle entrance is connected with calcium carbide particle outlet；Benzene reactor processed has acetylene entrance, carbon dioxide entrance, carbon monoxide inlet, hydrogen inlet, methane entrance and benzene product exit.The system, which can be realized, prepare benzene using coal maximization, so as to realize from the coal of low value to the conversion of high added value benzene.
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：
Low-order coal breaker, the low-order coal breaker has low-order coal entrance and low-order coal dust outlet；
There is preheating zone in limekiln, the limekiln and area is fired, the preheating zone has lime stone entrance, the burning
There is quick lime to export and carbon dioxide outlet in area processed；
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；
Press ball device, the press ball device has low-order coal powdering inlet, quick lime powder entrance and the outlet of material pelletizing,
The low-order coal powdering inlet is connected with the low-order coal dust outlet, the quick lime powder entrance and the quick lime powder
Outlet is connected；
Revolving bed pyrolysis installation, the revolving bed pyrolysis installation has material pelletizing entrance, the outlet of pyrolysis pelletizing, coal tar
Outlet and pyrolysis gas outlet, the material pelletizing entrance are connected with material pelletizing outlet；
Furnace of calcium carbide, the furnace of calcium carbide has pyrolysis pelletizing entrance, calcium carbide outlet and carbon monoxide outlet, the pyrolysis pelletizing
Entrance is connected with the pyrolysis 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 in the limekiln, an oxygen of the carbon monoxide inlet and the furnace of calcium carbide
Change carbon outlet to be connected, pyrolysis gas outlet of hydrogen inlet and the methane entrance respectively with the revolving bed pyrolysis installation is connected；
Separator, the separator have benzene product inlet, ethene outlet and benzene outlet, the benzene product inlet with
The benzene product exit is connected.
Optionally, said system further comprises：Purification separation device, the purification separation device is arranged on the rotation
Between the bed pyrolysis gas outlet of pyrolysis installation and the hydrogen inlet and methane entrance of the acetylene benzene reactor, the purification point
It is suitable to isolate the hydrogen and methane in the pyrolysis gas from device.
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：Low-order coal breaker 100, limekiln 200, quick lime are crushed
Device 300, press ball device 400, revolving bed pyrolysis installation 500, furnace of calcium carbide 600, calcium carbide crushing device 700, acetylene generator
800th, acetylene benzene reactor 900 and separator 1000.
Wherein, low-order coal breaker 100 has low-order coal entrance 110 and low-order coal dust outlet 120；
There is preheating zone 210 in limekiln 200 and area 220 is fired, preheating zone 210 has lime stone entrance 201, fires area
220 have quick lime outlet 202 and carbon dioxide outlet 203；
Quick lime breaker 300 have quick lime entrance 310 and quick lime powder outlet 320, quick lime entrance 310 with
Quick lime outlet 202 is connected；
Press ball device 400 has low-order coal powdering inlet 410, quick lime powder entrance 420 and material pelletizing outlet 430,
Low-order coal powdering inlet 410 is connected with low-order coal dust outlet 120, quick lime powder entrance 420 and quick lime powder outlet 320
It is connected；
Revolving bed pyrolysis installation 500 has material pelletizing entrance 510, pyrolysis pelletizing outlet 520, the and of coal tar oil export 530
Pyrolysis gas outlet 540, material pelletizing entrance 510 is connected with material pelletizing outlet 430；
Furnace of calcium carbide 600 has pyrolysis pelletizing entrance 610, calcium carbide outlet 620 and carbon monoxide outlet 630, and pyrolysis pelletizing enters
Mouth 610 is connected with pyrolysis pelletizing outlet 540；
Calcium carbide crushing device 700 has calcium carbide entrance 710 and calcium carbide particle outlet 720, and calcium carbide entrance 710 is exported with calcium carbide
620 are connected；
Acetylene generator 800 has calcium carbide particle entrance 810, water inlet 820 and acetylene outlet 830, calcium carbide particle entrance
810 are connected with calcium carbide particle outlet 720；
Benzene reactor 900 processed has acetylene entrance 910, carbon dioxide entrance 920, carbon monoxide inlet 930, hydrogen inlet
940th, methane entrance 950 and benzene product exit 960, acetylene entrance 910 are connected with the acetylene outlet 830 of acetylene generator 800, and two
Carbonoxide entrance 920 is connected with the carbon dioxide outlet 203 in limekiln 200, carbon monoxide inlet 930 and the one of furnace of calcium carbide 600
Carbon oxide outlet 630 is connected, the pyrolysis gas outlet of hydrogen inlet 940 and methane entrance 950 respectively with revolving bed pyrolysis installation 500
530 are connected；
Separator 1000 has benzene product inlet 1010, ethene outlet 1020 and benzene outlet 1030, benzene product inlet
1010 are connected with benzene product exit 960.
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, pressure ball after low-order coal powder is mixed with quick lime powder, then carry out subsequent reactions, is significantly improved
The contact area of coal and quick lime, improves reaction efficiency, and caking property in itself that have using low-order coal reduces the difficulty of pressure ball
Degree；In addition, low-order coal and quick lime pelletizing, which enter revolving bed pyrolysis installation, is pyrolyzed upgrading, pyrolysis is more efficient, and gaseous product can
It is used as fuel gas and acetylene benzene reactor feed gas；Upgraded coal produces calcium carbide with quick lime, prepares acetylene, is used as benzene reactor processed
Unstripped gas, realize low-order coal clean and effective utilize.Therefore, benzene is prepared by low-order coal using the utility model embodiment
System can realize and prepare benzene using fine coal maximization, the yield of benzene is drastically increased, so as to realize the coal from low value
To the conversion of the benzene of high added value, 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 fine coal of the utility model specific embodiment is described in detail below with reference to Fig. 1.
Low-order coal breaker 100
According to embodiment of the present utility model, low-order coal breaker 100 has low-order coal entrance 110 and low-order coal powder
Outlet 120.Thus, low-order coal is subjected to break process after drying, to obtain low-order coal powder.
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 pyrolysis 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 reaction, the fuel gas such as remaining carbon monoxide, light hydrocarbons can be each step combustion chamber or add
Hot stove provides thermal source, realizes effective utilization of resource.
According to embodiment of the present utility model, the average grain diameter of low-order coal powder is less than 20 microns, preferably less than 10 microns.
Thus low-order coal and the contact area of quick lime can be significantly improved by low-order coal being crushed to below micron level, while can show
Writing reduces the energy consumption of reaction of the two, is easier to make for calcium carbide reaction.
Limekiln 200
According to embodiment of the present utility model, there is preheating zone 210 in limekiln 200 and area 220, preheating zone 210 is fired
With lime stone entrance 201, firing area 220 has quick lime outlet 202 and carbon dioxide outlet 203.Thus, lime stone is existed
Processing is fired in limekiln, to obtain quick lime and carbon dioxide.Lime stone, which is that calcium carbonate content is higher, (typically to exist
More than 97%), the less lime stone of impurity.
Quick lime breaker 300
According to embodiment of the present utility model, quick lime breaker 300 has quick lime entrance 310 and quick lime powder
Outlet 320, quick lime entrance 310 is connected with quick lime outlet 202.Thus, quick lime is subjected to break process, to be given birth to
Lime powder.
According to embodiment of the present utility model, quick lime is crushed to average grain diameter less than 20 microns, preferably 10 microns with
Under.Thus low-order coal and the contact area of quick lime can be significantly improved by calcium lime powder being broken to below micron level, while energy
The energy consumption of reaction of the two is enough significantly reduced, calcium carbide reaction is easier to make for.
Press ball device 400
According to embodiment of the present utility model, there is press ball device 400 low-order coal powdering inlet 410, quick lime powder to enter
Mouth 420 and material pelletizing outlet 430, low-order coal powdering inlet 410 is connected with low-order coal dust outlet 120, and quick lime powder enters
Mouth 420 is connected with quick lime powder outlet 320.Thus, low-order coal powder and quick lime powder are subjected to mixing and pressure ball are handled,
To obtain material pelletizing.Inventor's discovery, pressure ball after low-order coal powder is mixed with quick lime powder, then carry out follow-up anti-
Should, the contact area of coal and quick lime is significantly improved, reaction efficiency is improved, while the bonding having in itself using low-order coal
Property, reduce the difficulty of pressure ball.
According to embodiment of the present utility model, the mass ratio of low-order coal powder and quick lime powder is 1：(1.1-1.4).It is low
When rank 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.Thus by the grain of material pelletizing
Footpath is controlled within the above range, advantageously in heat transfer, improves the thermal efficiency.
Revolving bed pyrolysis installation 500
According to embodiment of the present utility model, revolving bed pyrolysis installation 500 has material pelletizing entrance 510, pyrolysis pelletizing
Outlet 520, coal tar oil export 530 and pyrolysis gas outlet 540, material pelletizing entrance 510 are connected with material pelletizing outlet 430.By
This, material pelletizing is supplied pyrolysis processing is carried out to revolving bed pyrolysis installation, to obtain pyrolysis pelletizing, coal tar and to contain
Hydrogen, methane, the pyrolysis gas of carbon monoxide and light hydrocarbons.
According to embodiment of the present utility model, material pelletizing feeding revolving bed pyrolysis installation carries out pyrolysis processing.According to this
The specific embodiment of utility model, the temperature of pyrolysis processing is 600-800 degrees Celsius, and the time is 1-2 hours.After pyrolysis
Pyrolysis gas to pyrolysis pelletizing, coal tar and containing hydrogen, methane, carbon monoxide and light hydrocarbons.Wherein methane and hydrogen can
As the raw material of acetylene benzene reaction in step S800, the fuel gas such as remaining carbon monoxide, light hydrocarbons can be each step
Combustion chamber or heating furnace provide thermal source, realize effective utilization of resource.
Furnace of calcium carbide 600
According to embodiment of the present utility model, furnace of calcium carbide 600 has pyrolysis pelletizing entrance 610, calcium carbide outlet 620 and an oxygen
Change carbon outlet 630, pyrolysis pelletizing entrance 610 is connected with pyrolysis pelletizing outlet 540.Thus, pyrolysis pelletizing is supplied to furnace of calcium carbide
Interior progress calcium carbide reaction, to obtain calcium carbide and carbon monoxide.
Calcium carbide crushing device 700
According to embodiment of the present utility model, there is calcium carbide crushing device 700 calcium carbide entrance 710 and calcium carbide particle to export
720, calcium carbide entrance 710 is connected with calcium carbide outlet 620.
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 800
According to embodiment of the present utility model, acetylene generator 800 has calcium carbide particle entrance 810, water inlet 820 and second
Alkynes outlet 830, calcium carbide particle entrance 810 is connected with calcium carbide particle outlet 720.Thus, calcium carbide is occurred in acetylene after crushing
Reacted in device with water, to obtain acetylene.
Benzene reactor 900 processed
According to embodiment of the present utility model, benzene reactor 900 processed has an acetylene entrance 910, carbon dioxide entrance 920,
Carbon monoxide inlet 930, hydrogen inlet 940, methane entrance 950 and benzene product exit 960, acetylene entrance 910 occur with acetylene
The acetylene outlet 830 of device 800 is connected, and carbon dioxide entrance 920 is connected with the carbon dioxide outlet 203 in limekiln 200, an oxidation
The carbon monoxide outlet 630 of carbon entrance 930 and furnace of calcium carbide 600 is connected, hydrogen inlet 940 and methane entrance 950 respectively with rotation
The pyrolysis gas outlet 530 of bed pyrolysis installation 500 is connected.
Thus, hydrogen and methane, limekiln 200 in the pyrolysis gas that will be produced in acetylene, revolving bed pyrolysis installation 500 are produced
The carbon monoxide produced in raw carbon dioxide and furnace of calcium carbide 600 is passed through in benzene reactor 900 processed and reacted, to obtain
Obtain benzo by-product ethene.
It will be appreciated to those of skill in the art that benzene reactor 900 processed is made up of heating furnace and at least one quartz ampoule,
And there is flat-temperature zone in heating furnace, above-mentioned mixed gas enters heating furnace flat-temperature zone by quartzy tube inlet, and benzene is obtained by reaction
And 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 1000
According to embodiment of the present utility model, there is separator 1000 benzene product inlet 1010, ethene to export 1020 and
Benzene outlet 1030, benzene product inlet 1010 is connected with benzene product exit 960.Separator 1000 is suitable to benzene reactor 900 processed
The benzene of middle acquisition and the ethylene separation of by-product.
Purification separation device 1100
According to specific embodiment of the utility model, said system also includes：Purification separation device 1100, purification separation dress
Put 1100 and be arranged on the pyrolysis gas outlet 530 of revolving bed pyrolysis installation 500 and the hydrogen inlet 940 of benzene reactor 900 processed and first
Between alkane entrance 950, purification separation device 1100 is suitable to isolate the hydrogen and methane in pyrolysis gas.
Thus, one of following advantages are at least had according to the system for preparing benzene by low-order coal of the utility model 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) pressure ball after low-order coal powder is mixed with quick lime powder, then subsequent reactions are carried out, significantly improve coal and life
The contact area of lime, improves reaction efficiency, reduces system energy consumption.
(3) low-order coal and quick lime pelletizing are pyrolyzed upgrading, gaseous product can react former as fuel gas and acetylene benzene
Expect gas；Upgraded coal produces calcium carbide with quick lime, prepares acetylene, as the unstripped gas of benzene reactor processed, realizes the clear of low-order coal
Clean efficient utilization.
(4) pyrolysis efficiency can be improved as pyrolysis installation using the revolving bed of heat accumulating type.
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) low-order coal is dried and
Break process, to obtain low-order coal powder；(2) lime stone is fired to processing in limekiln, to obtain quick lime
And carbon dioxide；(3) quick lime is subjected to break process, to obtain quick lime powder；(4) by low-order coal powder and quick lime
Powder carries out mixing and pressure ball processing, to obtain material pelletizing；(5) material pelletizing is supplied to revolving bed pyrolysis installation
Row pyrolysis processing, to obtain being pyrolyzed pelletizing, coal tar and pyrolysis gas containing hydrogen, methane, carbon monoxide and light hydrocarbons；
(6) pyrolysis pelletizing is supplied to furnace of calcium carbide and carries out calcium carbide reaction, to obtain calcium carbide and carbon monoxide；(7) by calcium carbide through broken
Reacted afterwards in acetylene generator with water, to obtain acetylene；And (8) by acetylene, step (5) produce pyrolysis gas in hydrogen
The carbon monoxide that the carbon dioxide and step (6) that gas and methane, step (2) are produced are produced is passed through in acetylene benzene reactor simultaneously
React, to obtain benzo by-product ethene.
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, pressure ball after low-order coal powder is mixed with quick lime powder, then carry out subsequent reactions, is significantly improved
The contact area of coal and quick lime, improves reaction efficiency, and caking property in itself that have using low-order coal reduces the difficulty of pressure ball
Degree；In addition, low-order coal and quick lime pelletizing, which enter revolving bed pyrolysis installation, is pyrolyzed upgrading, pyrolysis is more efficient, and gaseous product can
It is used as fuel gas and acetylene benzene reactor feed gas；Upgraded coal produces calcium carbide with quick lime, prepares acetylene, is used as benzene reactor processed
Unstripped gas, realize low-order coal clean and effective utilize.Therefore, benzene is prepared by low-order coal using the utility model embodiment
Method can realize and prepare benzene using fine coal maximization, the yield of benzene is drastically increased, so as to realize the coal from low value
To the conversion of the benzene of high added value, and have the advantages that flow is simple, 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：Low-order coal break process
According to embodiment of the present utility model, low-order coal is dried and break process, to obtain low-order coal powder.
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 pyrolysis 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 reaction, the fuel gas such as remaining carbon monoxide, light hydrocarbons can be each step combustion chamber or add
Hot stove provides thermal source, realizes effective utilization of resource.
According to embodiment of the present utility model, the average grain diameter of low-order coal powder is less than 20 microns, preferably less than 10 microns.
Thus low-order coal and the contact area of quick lime can be significantly improved by low-order coal being crushed to below micron level, while can show
Writing reduces the energy consumption of reaction of the two, is easier to make for calcium carbide reaction.
S200：Lime stone firing is handled
According to embodiment of the present utility model, lime stone is fired to processing in limekiln, to obtain quick lime
And carbon dioxide.Lime stone is that calcium carbonate content is higher (typically more than 97%), the less lime stone of impurity.
S300：Quick lime break process
According to embodiment of the present utility model, quick lime is subjected to break process, to obtain quick lime powder.
According to embodiment of the present utility model, quick lime is crushed to average grain diameter less than 20 microns, preferably 10 microns with
Under.Thus low-order coal and the contact area of quick lime can be significantly improved by calcium lime powder being broken to below micron level, while energy
The energy consumption of reaction of the two is enough significantly reduced, calcium carbide reaction is easier to make for.
S400：Mixing and pressure ball processing
According to embodiment of the present utility model, low-order coal powder and quick lime powder are subjected to mixing and pressure ball is handled, with
Just material pelletizing is obtained.Inventor has found, pressure ball after low-order coal powder is mixed with quick lime powder, then carries out subsequent reactions,
The contact area of coal and quick lime is significantly improved, reaction efficiency is improved, while the caking property having in itself using low-order coal,
Reduce the difficulty of pressure ball.
According to embodiment of the present utility model, the mass ratio of low-order coal powder and quick lime powder is 1：(1.1-1.4).It is low
When rank 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.Thus by the grain of material pelletizing
Footpath is controlled within the above range, advantageously in heat transfer, improves the thermal efficiency.
S500：Pyrolysis processing in revolving bed pyrolysis installation
According to embodiment of the present utility model, material pelletizing is supplied pyrolysis processing is carried out to revolving bed pyrolysis installation,
To obtain being pyrolyzed pelletizing, coal tar and pyrolysis gas containing hydrogen, methane, carbon monoxide and light hydrocarbons.
According to embodiment of the present utility model, material pelletizing feeding revolving bed pyrolysis installation carries out pyrolysis processing.According to this
The specific embodiment of utility model, the temperature of pyrolysis processing is 600-800 degrees Celsius, and the time is 1-2 hours.After pyrolysis
Pyrolysis gas to pyrolysis pelletizing, coal tar and containing hydrogen, methane, carbon monoxide and light hydrocarbons.Wherein methane and hydrogen can
As the raw material of acetylene benzene reaction in step S800, the fuel gas such as remaining carbon monoxide, light hydrocarbons can be each step
Combustion chamber or heating furnace provide thermal source, realize effective utilization of resource.
S600：Prepare calcium carbide
According to embodiment of the present utility model, pyrolysis pelletizing is supplied to furnace of calcium carbide and carries out calcium carbide reaction, 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 pyrolysis gas that acetylene, step S500 are produced
The carbon monoxide that the carbon dioxide and step S600 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) pressure ball after low-order coal powder is mixed with quick lime powder, then subsequent reactions are carried out, significantly improve coal and life
The contact area of lime, improves reaction efficiency, reduces system energy consumption.
(3) low-order coal and quick lime pelletizing are pyrolyzed upgrading, gaseous product can react former as fuel gas and acetylene benzene
Expect gas；Upgraded coal produces calcium carbide with quick lime, prepares acetylene, as the unstripped gas of benzene reactor processed, realizes the clear of low-order coal
Clean efficient utilization.
(4) pyrolysis efficiency can be improved as pyrolysis installation using the revolving bed of heat accumulating type.
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
The lime and middle low-order coal that limekiln is obtained are crushed to less than 20 μm, by lime and middle low-order coal in mass ratio
1.1:1 mixing, adds appropriate binding agent, carries out pressure ball, a diameter of 10~40mm of control pelletizing.By pelletizing feeding revolving bed pyrolysis
Device, pyrolysis temperature is 800 DEG C, and pyrolysis time is 1h.Obtained pyrolysis pelletizing hot charging enters furnace of calcium carbide production calcium carbide.Produced
Calcium carbide cooling crush, by the size controlling of calcium carbide between 50~80mm, reaction obtains acetylene into acetylene generator.By
Low-order coal can obtain 370kg or so acetylene, 95kg or so hydrogen, 204kg with 2050kg lime stones in the system, 1000kg
Methane, 800kg carbon dioxide and the 420kg carbon monoxide of left and right.Acetylene, hydrogen, methane, carbon dioxide and the 199kg of gained
Carbon monoxide, which is passed through in acetylene benzene reactor, to be reacted, and the reaction time of gaseous mixture is 10s, and reaction temperature is
900 DEG C, reactor uses the tube bank being made up of internal diameter for 4mm quartz ampoule, and reactor flat-temperature zone is 300mm.Production is obtained
185kg benzene and 107kg 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 (2)
1. a kind of system that benzene is prepared by low-order coal, it is characterised in that including：
Low-order coal breaker, the low-order coal breaker has low-order coal entrance and low-order coal dust outlet；
There is preheating zone in limekiln, the limekiln and area is fired, the preheating zone has lime stone entrance, the firing area
With quick lime outlet and carbon dioxide outlet；
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；
Press ball device, the press ball device has low-order coal powdering inlet, quick lime powder entrance and the outlet of material pelletizing, described
Low-order coal powdering inlet is connected with the low-order coal dust outlet, and the quick lime powder entrance is exported with the quick lime powder
It is connected；
Revolving bed pyrolysis installation, the revolving bed pyrolysis installation has material pelletizing entrance, the outlet of pyrolysis pelletizing, coal tar oil export
And pyrolysis gas outlet, the material pelletizing entrance is exported with the material pelletizing to be connected；
Furnace of calcium carbide, the furnace of calcium carbide has pyrolysis pelletizing entrance, calcium carbide outlet and carbon monoxide outlet, the pyrolysis pelletizing entrance
It is connected with the pyrolysis 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 in the limekiln to be connected, the carbon monoxide of the carbon monoxide inlet and the furnace of calcium carbide
Outlet is connected, and the pyrolysis gas outlet of the hydrogen inlet, methane entrance respectively with the revolving bed pyrolysis installation is connected；
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 further comprise：Purification separation is filled
Put, the purification separation device is arranged on the pyrolysis gas outlet and the acetylene benzene reactor of the revolving bed pyrolysis installation
Between hydrogen inlet and methane entrance, the purification separation device is suitable to isolate the hydrogen and methane in the pyrolysis gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621361136.6U CN206318896U (en) | 2016-12-12 | 2016-12-12 | The system that benzene is prepared by low-order coal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621361136.6U CN206318896U (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 |
|---|---|
| CN206318896U true CN206318896U (en) | 2017-07-11 |
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| Country | Link |
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2016
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