CN105967965B - A kind of lower carbon number hydrocarbons fluid bed aromatisation device and application - Google Patents
A kind of lower carbon number hydrocarbons fluid bed aromatisation device and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to lower carbon number hydrocarbons to produce aromatic hydrocarbons technical field, and in particular to a kind of lower carbon number hydrocarbons fluid bed aromatisation device and application.Described device is made of fluid bed aromatization reactor, aromatic hydrocarbons gas-liquid separator, conversion of methane device, methyl alcohol synthetic reactor, gas-liquid separator, methyl alcohol vaporizing device, dehydrogenation reactor etc..Aromatization method of the present invention, production cost is low, and aromatisation high conversion rate reduces cycle up to 99.9%.
Description
Technical field
The invention belongs to lower carbon number hydrocarbons to produce aromatic hydrocarbons technical field, and in particular to a kind of lower carbon number hydrocarbons fluid bed aromatisation device and
Using.
Background technology
Currently, the techniques such as the FCC of China's oil chemical industry, thermal cracking, delayed coking generate a large amount of cracking dry gas, and these
It cracks most of dry gas and is used as fuel gas and civil liquefied gas after isolation, utility value is low, pollutes environment, pole is caused to resource
Big waste.With the raising of refining capacity, the yield for cracking dry gas is also increasing year by year；Coal chemical technology is fast-developing,
Also along with some refinery gas while producing purpose product, and with the increase of the cycle-index in system, dry gas amount by
It is cumulative big, inhibit the progress of main reaction, it is necessary to which outer row to cause environmental pollution, wastage of material, and increases cost.
At the same time, with the development of national economy, the aromatic hydrocarbons import volume as important industrial chemicals increasingly increases, these
Value can be improved after being converted as byproduct, reduced pollution, can also be alleviated the imbalance between supply and demand of China's aromatic production, make resource
Rationally applied.
Patent CN103328417A disclose produce benzene and ethylene from lower paraffin hydrocarbon there is relatively low fund and operating cost
Integral method.The patent does not carry out the hydrogen that cannot be converted in dry gas and methane separation to convert valuable reaction original
Material, leads to the cycle with reaction, and the amount of hydrogen and methane is increasing, there is the tripe phenomenon that rises, need to lead to the operation of device
Discharge torch is crossed to solve, causes unnecessary waste.
Patent CN00122963.X discloses a kind of low-carbon hydrocarbon aromatization method, after low-carbon hydrocarbon raw material is heated, enters
Contact and carry out aromatization in fixed bed reactors with catalyst, reaction product obtained after being cooled and separated BTX aromatics,
Hydrogen and high quality liquefied gas；It is characterized in that reaction temperature is 500~600 DEG C, catalyst is with HZSM-5 zeolites and aluminium oxide
Carrier, using nickel and zinc as active metal component.The reaction temperature of the invention is high, and catalyst regeneration energy consumption is big, after reaction in product
There are a large amount of dry gas and liquefied gas, aromatic hydrocarbons cannot be converted into, and equipment investment is big, market competitiveness is poor.
Patent CN103058814B discloses a kind of method producing aromatic hydrocarbons and alkene using liquefied gas, and liquefied gas is being catalyzed
It is reacted under the action of agent, after isolating propane and butane and dehydrogenation, propylene and isobutene is made.The raw material of the invention is C3, C4,
Do not include C2, the further aromatisation of alkene is not converted to the aromatic hydrocarbons with high added value, econmics comparison is poor yet.
Invention content
The object of the present invention is to provide a kind of lower carbon number hydrocarbons fluid bed aromatisation device and application, specific technical solution are as follows：
A kind of lower carbon number hydrocarbons fluid bed aromatisation device, in described device, raw material preheating stove 1, fluid bed aromatization reactor
2, aromatic hydrocarbons gas-liquid separator 3, pressure-variable adsorption separator 4, absorption tower 5 are sequentially connected；And divide from absorption tower 5 for two-way：All the way according to
It is secondary after conversion of methane device 6, methyl alcohol synthetic reactor 7, gas-liquid separator 8, methyl alcohol vaporizing device 9, with 1 phase of raw material preheating stove
Even, first circulation loop is formed；Another way is successively after lower carbon number hydrocarbons preheating furnace 10, dehydrogenation reactor 11, with raw material preheating
Stove 1 is connected, and forms second circulation loop.
The method for carrying out aromatization of low carbon hydrocarbon using device as described above：
Mixing lower carbon number hydrocarbons 12 preheats laggard fluidized bed aromatization reactor 2 through raw material preheating stove 1 and aromatization occurs,
It being detached through aromatic hydrocarbons gas-liquid separator 3, obtained liquid phase is aromatic hydrocarbon product 16, and obtained gas phase enters pressure-variable adsorption separator 4,
Adsorbing separation goes out hydrogen 14, remaining gas phase fully enters absorption tower 5, and top and bottom two-way is divided into after the absorption of absorbent 13,
This is divided into all the way as two-way at top, only containing methane obtained after conversion of methane device 6, methyl alcohol synthetic reactor 7 all the way contain first
The mixture of alcohol and fixed gas 15, and gasify through 8 isolated Liquid Phase Methanol of gas-liquid separator, then through methyl alcohol vaporizing device 9, it obtains
Gas-phase methanol；The hydrogen 14 that adsorbing separation goes out in the another way only gas phase containing methane and pressure-variable adsorption separator 4 is produced as LNG
Product 17；Bottom this lower carbon number hydrocarbons of methane is stripped of in adsorption tower 5 all the way after lower carbon number hydrocarbons preheating furnace 10 and dehydrogenation reactor 11
Unsaturated low-carbon alkene is obtained, into fluidized bed aromatization reactor 2 together with the gas-phase methanol by raw material preheating stove 1, into
Enter next cycle；
14 1 tunnel of hydrogen that adsorbing separation goes out in pressure-variable adsorption separator 4 turns into methane together with the methane isolated
Change reactor 6；Another way hydrogen 14 is used as hydrogen product.
Preferably, mixing lower carbon number hydrocarbons 12 is first successively through lower carbon number hydrocarbons preheating furnace 10 and dehydrogenation reactor 11, in dehydrogenation reactor
Fluid bed aromatization reactor 2 is entered back into 11 after dehydrogenation, participates in circular response.
Further, the reaction temperature of fluid bed aromatization reactor is 350~540 DEG C, and pressure is 0.1~3MPa, hydrocarbon
The mass space velocity of class raw material is 0.2~80h-1。
Further, in first time recycles, each composition and volume content that mix in lower carbon number hydrocarbons are：Hydrogen 0~20%,
Methane 0~15%, ethane 0~10%, ethylene 0~15%, propane 0~40%, propylene 0~10%, butane 0~20%, butylene 0
~5%, pentane 0~6%, amylene 0~4%, C6+0~5%.
When aromatization occurring in fluid bed aromatization reactor 2, used catalyst is by metal salt, molecule
Sieve, P elements modifying agent, rare-earth metal modified dose and structure reinforcing agent composition, this mass fraction of five kinds of components in the catalyst
It is followed successively by 0.1%~10%, 20%~60%, 0~5%, 0~5% and 30%~70%.
Metallic element in the metal salt is one kind in zinc, silver, gallium, molybdenum, tungsten, copper, manganese, nickel, iron, platinum and chromium
Or more than one；Molecular sieve is one or both of ZSM-5 molecular sieve and ZSM-11 molecular sieves, and rare-earth element modified dose is lanthanum
One or both of with Ce elements, structure reinforcing agent is in aluminium oxide, silica, boehmite, kaolin and diatomite
One or more.
The grain size of the catalyst is 10~300 μm, and average grain diameter is 60~150 μm.
The preparation method of the catalyst is：Molecular sieve and structure reinforcing agent are configured to mixed slurry, made by spraying
Grain obtains composite particles, and is roasted in muffle furnace；Metal salt, P elements modifying agent and rare-earth metal modified dose are configured to mix
Solution is closed, and roasting composite particles are stirred into dipping wherein, drying, roasting obtain the fluidization catalyst.
The beneficial effects of the invention are as follows：
(1) aromatization method of the present invention, production cost is low, and aromatisation high conversion rate reduces cycle up to 99.9%,
Conversion is that purpose product volume is more；
(2) present invention converts after alkene lower carbon number hydrocarbons to carries out aromatisation again, greatly reduces reaction temperature and improves
Conversion ratio, alkyl reaction are the endothermic reactions, and methanol reaction is exothermic reaction, and methane is changed into after methanol and is total to unsaturated lower carbon number hydrocarbons
Same mixed feeding reduces energy consumption, is conducive to the balanced use of heat；
(3) in the present invention, methane and hydrogen that cycle reaction generates can continue to be converted into methanol, realize closed cycle,
Raw material is maximally utilized；
(4) methane does not convert in a fluidized bed reactor or conversion ratio is very low, and the present invention is completely converted into methane can
With the methanol of conversion, methanol enters aromatization reactor after vaporizer gasifies, and the high aromatic hydrocarbons of volume increase added value has obtained resource
Reasonable utilization.
(5) being saturated the carbon content for entering aromatization reactor post catalyst reaction after lower carbon number hydrocarbons dehydrogenation has apparent increase,
Be conducive to maintain the charcoal temperature of regenerator.
Description of the drawings
Fig. 1 is the process flow diagram mixed when lower carbon number hydrocarbons is directly entered raw material preheating stove participation circular response；
Fig. 2 be mixing lower carbon number hydrocarbons first through dehydrogenation reactor dehydrogenation, entering back into fluid bed aromatization reactor, to participate in cycle anti-
Seasonable process flow diagram；
The concrete meaning respectively numbered in figure is as follows：1- raw material preheating stoves, 2- fluid bed aromatization reactors, 3- aromatic hydrocarbons gas-liquids
Separator, 4- pressure-variable adsorption separators, the absorption towers 5-, 6- conversion of methane devices, 7- methyl alcohol synthetic reactors, 8- gas-liquid separators,
9- liquid vaporizers, 10- lower carbon number hydrocarbons preheating furnaces, 11- dehydrogenation reactors, 12- mixing lower carbon number hydrocarbons, 13- absorbents, 14- hydrogen,
15- fixed gases, 16- aromatic hydrocarbon products, 17-LNG products.
Specific implementation mode
The invention discloses a kind of lower carbon number hydrocarbons fluid bed aromatisation device and applications, with reference to the accompanying drawings and examples to this
Invention is described further.
In the aromatization of low carbon hydrocarbon device, raw material preheating stove 1, fluid bed aromatization reactor 2, aromatic hydrocarbons gas-liquid separator
3, pressure-variable adsorption separator 4, absorption tower 5 are sequentially connected；And divide from absorption tower 5 for two-way：It is anti-to pass through methane conversion successively all the way
After answering device 6, methyl alcohol synthetic reactor 7, gas-liquid separator 8, methyl alcohol vaporizing device 9, it is connected with raw material preheating stove 1, forms first cycle
Circuit；Another way after lower carbon number hydrocarbons preheating furnace 10, dehydrogenation reactor 11, is connected successively with raw material preheating stove 1, forms second
Circulation loop；
The fluidization catalyst is positioned in fluid bed aromatization reactor 2.
Embodiment 1
ZSM-5 molecular sieve and kaolin, Aluminum sol are configured to mixed slurry, composite particles are obtained by mist projection granulating,
The composite particles made are put into muffle furnace within specified temperatures and are roasted.By active metal mixed solution and roasting answer
Particle stirring dipping drying is closed, specific roasting temperature is reset and is kept for a few hours, final catalyst, this catalyst is made
For the special catalyst of aromatisation.
Embodiment 2
The catalyst 880g that embodiment 1 obtains is weighed, is fitted into fluid bed aromatization reactor 2.
The mixing lower carbon number hydrocarbons 12 of composition, content, it is anti-to preheat laggard fluidized bed aromatisation through raw material preheating stove 1 shown in table 1
It answers device 2 that aromatization occurs, is detached through aromatic hydrocarbons gas-liquid separator 3, obtained liquid phase is aromatic hydrocarbon product 16, obtained gas phase
Into pressure-variable adsorption separator 4, adsorbing separation goes out hydrogen 14, remaining gas phase fully enters absorption tower 5, after the absorption of absorbent 13
Be divided into top and bottom two-way, this is divided into all the way as two-way at top, only containing methane all the way through conversion of methane device 6, first
The mixture containing methanol and fixed gas 15 is obtained after alcohol synthetic tower 7, and through 8 isolated Liquid Phase Methanol of gas-liquid separator, then pass through
Methyl alcohol vaporizing device 9 gasifies, and obtains gas-phase methanol；Absorption point in the another way only gas phase containing methane and pressure-variable adsorption separator 4
The hydrogen 14 separated out is used as LNG product 17；This lower carbon number hydrocarbons for being stripped of methane in adsorption tower 5 all the way of bottom is preheated through lower carbon number hydrocarbons
Unsaturated low-carbon alkene is obtained after stove 10 and dehydrogenation reactor 11, into becoming a mandarin together with the gas-phase methanol by raw material preheating stove 1
Change bed aromatization reactor 2, into next cycle；In the gaseous phase outlet sampling analysis of aromatic hydrocarbons gas-liquid separator 3, liquid-phase outlet
Sampling calculates aromatics yield, and post catalyst reaction is taken to analyze carbon content online below fluid bed aromatization reactor 2.
14 1 tunnel of hydrogen that adsorbing separation goes out in pressure-variable adsorption separator 4 turns into methane together with the methane isolated
Change reactor 6；Another way hydrogen 14 is used as hydrogen product.(as shown in Figure 1)
The reaction temperature of whole device is 375 DEG C, reaction pressure 0.3MPa, and the mass space velocity of hydrocarbon raw material is 0.5h-1。
Embodiment 3
The reaction temperature of whole device is 475 DEG C, other are same as Example 2.
Embodiment 4
The reaction temperature of whole device is 520 DEG C, other are same as Example 2.
Embodiment 5
The reaction temperature of whole device is 540 DEG C, other are same as Example 2.
In 1 embodiment 2-5 of table, the composition and content of lower carbon number hydrocarbons are mixed
The product of 2 embodiment 2-5 of table forms and corresponding mass fraction
| Product forms, w% | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Hydrogen | 20.84 | 27.42 | 35.28 | 46.07 |
| Methane | 13.96 | 15.3 | 21.73 | 28.83 |
| Ethane | 8.17 | 9.58 | 10.04 | 4.36 |
| Ethylene | 4.51 | 2.98 | 2.27 | 1.68 |
| Propane | 36.79 | 35.13 | 25.76 | 15.32 |
| Propylene | 3.01 | 1.59 | 1.04 | 0.94 |
| Butane | 9.06 | 5.17 | 1.79 | 1.47 |
| Butylene | 1.06 | 0.97 | 0.71 | 0.52 |
| Pentane | 1.65 | 0.59 | 0.86 | 0.47 |
| Amylene | 0.19 | 0.36 | 0.13 | 0.21 |
| C6+ | 0.76 | 0.91 | 0.39 | 0.13 |
| Aromatics yield (%) | 16.33 | 24.81 | 26.14 | 29.52 |
| Carbon content (%) | 1.24 | 1.57 | 1.76 | 1.98 |
Note：Product composition in table 2 refers to completing the product composition after first time aromatisation.
As shown in Table 2, alkene can be obtained by whole conversions at 520 DEG C or less；With the raising of reaction temperature, saturation
The conversion ratio of alkane increases, and the yield of hydrogen and methane is also significantly increased, and causes the investment of equipment and energy consumption to increase, therefore
By reaction temperature select at 520 DEG C hereinafter, and unsaturated olefin be easier to be converted into aromatic hydrocarbons.But methane is in fluidized-bed reactor 2
In do not convert, and the increase of hydrogen partial pressure can inhibit the progress of dehydrogenation reaction, so, it is technique institute to isolate hydrogen and methane
It must take into consideration.
Embodiment 6
The catalyst 880g that embodiment 1 obtains is weighed, is fitted into fluid bed aromatization reactor 2.
600g dehydrogenations (chromium-based catalysts, DeH-14) are weighed, are fitted into dehydrogenation reactor 11.
The composition and content of raw material mixing lower carbon number hydrocarbons are as shown in table 3, and mixing lower carbon number hydrocarbons 12 is preheated through lower carbon number hydrocarbons preheating furnace 10
Enter dehydrogenation reactor 11 afterwards and dehydrogenation reaction occurs, the unsaturated lower carbon number hydrocarbons after dehydrogenation is sent out into fluidized bed aromatization reactor 2
Raw aromatization, detaches, obtained liquid phase is aromatic hydrocarbon product 16, and obtained gas phase enters change through aromatic hydrocarbons gas-liquid separator 3
Adsorbing separation device 4 is pressed, adsorbing separation goes out hydrogen 14, remaining gas phase enters absorption tower 5, point top and bottom after the absorption of absorbent 13
Portion's two-way, this is divided into all the way as two-way at top, only containing methane all the way after conversion of methane device 6, methyl alcohol synthetic reactor 7
To the mixture containing methanol and fixed gas 15, and through 8 isolated Liquid Phase Methanol of gas-liquid separator, then through 9 gas of methyl alcohol vaporizing device
Change, obtains gas-phase methanol；The hydrogen 14 that adsorbing separation goes out in the another way only gas phase containing methane and pressure-variable adsorption separator 4 is made
For LNG product 17；Bottom this lower carbon number hydrocarbons of methane is stripped of in adsorption tower 5 all the way through lower carbon number hydrocarbons preheating furnace 10 and dehydrogenation reaction
Unsaturated low-carbon alkene is obtained after device 11, into fluidized bed aromatization together with the gas-phase methanol by raw material preheating stove 1
Device 2, into next cycle；In the gaseous phase outlet sampling analysis of aromatic hydrocarbons gas-liquid separator 3, liquid-phase outlet sampling calculates aromatic hydrocarbons and receives
Rate takes post catalyst reaction to analyze carbon content online below fluid bed aromatization reactor 2.
14 1 tunnel of hydrogen that adsorbing separation goes out in pressure-variable adsorption separator 4 turns into methane together with the methane isolated
Change reactor 6；Another way hydrogen 14 is used as hydrogen product.(as shown in Figure 2)
The reaction temperature of whole device is 375 DEG C, reaction pressure 0.3MPa, and the mass space velocity of hydrocarbon raw material is 0.5h-1。
Embodiment 7
The reaction temperature of whole device is 475 DEG C, other are same as Example 6.
Embodiment 8
The reaction temperature of whole device is 520 DEG C, other are same as Example 6.
Embodiment 9
The reaction temperature of whole device is 540 DEG C, other are same as Example 6.
In 3 embodiment 6-9 of table, the composition and content of lower carbon number hydrocarbons are mixed
The product of 4 embodiment 6-9 of table forms and corresponding mass fraction
Note：Product composition in table 4 refers to completing the product composition after first time aromatisation.
As can be seen from Table 4, reaction temperature reduces after dehydrogenation, and conversion ratio increases, and saturated alkane is converted into the yield of aromatic hydrocarbons
Increase, the amount of propane is significantly increased, this continues cycling through aromatisation volume increase aromatic hydrocarbons after being conducive to dehydrogenation, conversion ratio is improved, through experiment
Gained conversion ratio be not less than 60%, the selectivity (alkyl) of aromatic hydrocarbons 64% or more, while the carbon distribution content above catalyst compared with
It is significantly increased before dehydrogenation, 1.5% or more, contributes to the heat balance for maintaining regenerator.
Embodiment 10
Be passed through raw material preheating stove 1 raw material be crude carbinol, composition and content it is as shown in table 5, other with 2 phase of embodiment
Together.
Embodiment 11
Be passed through raw material preheating stove 1 raw material be crude carbinol, composition and content it is as shown in table 5, other with 3 phase of embodiment
Together.
Embodiment 12
Be passed through raw material preheating stove 1 raw material be crude carbinol, composition and content it is as shown in table 5, other with 4 phase of embodiment
Together.
Embodiment 13
Be passed through raw material preheating stove 1 raw material be crude carbinol, composition and content it is as shown in table 5, other with 5 phase of embodiment
Together.
In 5 embodiment 10-13 of table, it is passed through the composition and content of raw material preheating stove 1
The product of 6 embodiment 10-13 of table forms and corresponding mass fraction
Note：Product composition in table 6 refers to completing the product composition after first time aromatisation.
As can be seen from Table 6, when methanol feeding temperature is raised to 500 DEG C or more, gas phase yield increases, especially saturated alkane
Amount obviously increase, the charging reaction of simple methanol is suitble to temperature also at 500 DEG C hereinafter, feeding temperature model with unsaturated olefin
It encloses consistent；And the carbon content of catalyst is substantially reduced compared with unsaturated olefin charging, simple methanol aromatization in actual production in this way
Change catalyst regeneration and release shortage of heat to maintain charcoal temperature, so feeding with unsaturated low-carbon alkene and being substantially better than simple inspection
Go out charging.
Claims (7)
1. a kind of method carrying out aromatization of low carbon hydrocarbon using lower carbon number hydrocarbons fluid bed aromatisation device device, which is characterized in that
It is anti-through laggard fluidized bed aromatization reactor (2) the generation aromatisation of raw material preheating stove (1) preheating to mix lower carbon number hydrocarbons (12)
It answers, is detached through aromatic hydrocarbons gas-liquid separator (3), obtained liquid phase is aromatic hydrocarbon product (16), and obtained gas phase enters pressure-variable adsorption
Separator (4), adsorbing separation go out hydrogen (14), remaining gas phase enters absorption tower (5), are divided into top after absorbent (13) absorption
With bottom two-way, this is divided into all the way as two-way at top, only containing methane all the way through conversion of methane device (6), methanol-fueled CLC
The mixture containing methanol and fixed gas (15) is obtained after tower (7), and through gas-liquid separator (8) isolated Liquid Phase Methanol, then pass through
Methyl alcohol vaporizing device (9) gasifies, and obtains gas-phase methanol；It is inhaled in the another way only gas phase containing methane and pressure-variable adsorption separator (4)
The hydrogen (14) that Fufen separates out is used as LNG product (17)；This lower carbon number hydrocarbons for being stripped of methane in adsorption tower (5) all the way of bottom passes through
Unsaturated low-carbon alkene is obtained after lower carbon number hydrocarbons preheating furnace (10) and dehydrogenation reactor (11), with the gas by raw material preheating stove (1)
Phase methanol is together into fluidized bed aromatization reactor (2), into next cycle；
The hydrogen (14) that adsorbing separation goes out in pressure-variable adsorption separator (4) turns into methane with the methane isolated together all the way
Change reactor (6)；Another way hydrogen (14) is used as hydrogen product；The reaction temperature of the fluid bed aromatization reactor is 350
~540 DEG C, pressure is 0.1~3MPa, and the mass space velocity of hydrocarbon raw material is 0.2~80h-1。
2. according to the method described in claim 1, it is characterized in that, mixing lower carbon number hydrocarbons (12) is first successively through lower carbon number hydrocarbons preheating furnace
(10) and dehydrogenation reactor (11) fluid bed aromatization reactor (2), is entered back into after dehydrogenation in dehydrogenation reactor (11), is participated in
Circular response.
3. according to the method described in claim 1, it is characterized in that, in first time recycles, mix each in lower carbon number hydrocarbons (12)
Composition and volume content are：Hydrogen 0~20%, methane 0~15%, ethane 0~10%, ethylene 0~15%, propane 0~40%,
Propylene 0~10%, butane 0~20%, butylene 0~5%, pentane 0~6%, amylene 0~4%, C6+0~5%.
4. according to the method described in claim 1, it is characterized in that, aromatisation occurs in fluid bed aromatization reactor (2)
When reaction, used catalyst is by metal salt, molecular sieve, P elements modifying agent, rare-earth metal modified dose and structure reinforcing agent
Composition.
5. according to the method described in claim 4, it is characterized in that, metallic element in the metal salt be zinc, silver, gallium, molybdenum,
One or more in tungsten, copper, manganese, nickel, iron, platinum and chromium；Structure reinforcing agent is aluminium oxide, silica, intends thin water
One or more in aluminium stone, kaolin and diatomite.
6. according to the method described in claim 4, it is characterized in that, the grain size of the catalyst is 10~300 μm.
7. according to the method described in claim 4, it is characterized in that, the preparation method of the catalyst is：By molecular sieve and knot
Structure reinforcing agent is configured to mixed slurry, obtains composite particles by mist projection granulating, and roasted in muffle furnace；By metal salt, phosphorus
Element modifier and rare-earth metal modified dose are configured to mixed solution, and roasting composite particles are stirred dipping wherein,
Drying, roasting obtain the fluidization catalyst.
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| CN104326859A (en) * | 2014-09-03 | 2015-02-04 | 华电煤业集团有限公司 | System for preparing aromatic hydrocarbons from coal, and method thereof |
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| WO2006068800A2 (en) * | 2004-12-22 | 2006-06-29 | Exxonmobil Chemical Patents Inc. | Production of alkylated aromatic hydrocarbons from methane |
| CN103058814A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon and olefin from liquefied gas |
| CN103509601A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | Technological process for co-production of propane by aromatization of carbon tetrad-hydrocarbon |
| CN105531248A (en) * | 2013-10-08 | 2016-04-27 | 沙特基础工业公司 | Integrated process for converting methane to aromatics and other chemicals |
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