CN104628511A - Technology for oxidative transformation of methane into aromatic hydrocarbon - Google Patents
Technology for oxidative transformation of methane into aromatic hydrocarbon Download PDFInfo
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- CN104628511A CN104628511A CN201310556487.7A CN201310556487A CN104628511A CN 104628511 A CN104628511 A CN 104628511A CN 201310556487 A CN201310556487 A CN 201310556487A CN 104628511 A CN104628511 A CN 104628511A
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Abstract
The invention discloses a technology for oxidative transformation of methane into aromatic hydrocarbon. The steps include: letting a methane-containing raw material enter a fluidized bed reactor; or dividing the methane-containing raw material into two parts, and making the halogenation reaction product of one part of the methane-containing raw material and the other part of methane-containing raw material enter the fluidized bed reactor together to carry out oxidation reaction; letting the reaction product in the fluidized bed reactor enter a moving-bed reactor loaded with an aromatization catalyst to carry out aromatization reaction, performing gas-liquid separation on the moving-bed reactor reaction product, returning the gas into the fluidized bed reactor to undergo further reaction, and letting the liquid product enter an aromatic hydrocarbon separation system to obtain different aromatic hydrocarbon products. The technology provided by the invention can reduce the energy consumption of the reaction process, and refines the unreacted methane again so as to make full use of methane. The produced propylene, butylene and other hydrocarbons can also be transformed into high value-added aromatic hydrocarbon products.
Description
Technical field
The invention belongs to the field that methane oxidation conversion is aromatic hydrocarbons, particularly one uses three reactor assemblies, makes methane obtain the process integration process of ethene and aromatic hydrocarbons through methane pre-reaction and oxidation.
Background technology
Methane is the main component in Sweet natural gas, biogas, coal-seam gas, shale gas and combustible ice.As far back as the early 1980s, Keller and Bhasin just finds that methane directly can be transformed by oxidative coupling reaction and obtains ethene and ethane.The chemical stability of methane makes the chemical utilization of Sweet natural gas restricted greatly, and Methane Activation makes it to be converted into industrial chemicals, becomes C
1the emphasis in chemical research field.Direct selective oxidation preparing synthetic gas, partial oxidation methyl alcohol and formaldehyde and oxidative coupling (OCM) C processed is mainly contained in the research on utilization direction of scientific research field methane
2hydrocarbon.From nineteen eighty-two, Union Carbide Corporation announces that methane can since direct oxidation coupling obtains ethene and ethane, due to rise in oil price and the ethene importance on petrochemical industry, make the research in this field deepen continuously.To hundreds of screening of catalyst, some high reactivities, high C is developed through 40 Duo Jia laboratories in the world
2optionally catalyst system to O
2activation and methane conversion mechanism study widely, achieve gratifying progress, but C
2 +yield is difficult to more than 25%.The transformation efficiency of this process is lower, and products distribution is wider, rare ethylene product separation difficulty, makes cost too high, still can not become the course of industrialization can competed with oil alkene, has contained the development of this technology in industrial application.
At present, about methane oxidation conversion be aromatic hydrocarbons catalyst system exist shortcoming be: transformation efficiency is lower, products distribution is wider, rare ethylene product is separated also very difficult, seriously constrain the development of methane oxidation coupling technology, if the ethene that methane oxidation coupling produces can be made, without separation, make it to continue reaction and be converted into other products, then can break the chemical equilibrium of methane oxidation coupling, oxidative coupling of methane is carried out, thus improve methane conversion, reduce energy consumption, realize effective utilization of methane.
Application number be 99109587.1 Chinese patent disclose a kind of method and device of methane converting High-efficient Production ethene.This invention relates to the method and apparatus with methane converting High-efficient Production ethene.Its method steps is: 1) adopt common methane halogenation method to prepare methine halide; 2) hydrocracking process can be carried out in the halogenating reaction room of former the first step methane, enters in other reaction chamber and carry out after also methyl halide can being separated; The method is having under hydrogen existent condition, and by methine halide hydrocracking, to prepare the hydrocarbon polymer of high carbon number, its transformation efficiency can reach 20% to 80%.The method of wherein said methane halogenation methine halide is: any known methane halogenation technology can be adopted to be executed reality, as U.S.Pat No.2320274, No.4199533 etc.The vapour etc. of Sweet natural gas, synthetic natural gas, heavy oil or coal that raw material thing is methane gas or mixes with other hydrocarbons for methane.Wherein require that methane content mol wt is in the feed than more than 25%.This invention methane gas material used does not need purifying.For providing the initial material of halogenation also not need purifying containing halogen gas, only require the gas of fluorine-containing, chlorine, bromine, the iodine that can provide halogenation, mol wt ratio is no less than 25%.And can suppress generally to be difficult to the carbon black that blocks and tar generates.What the gas of its halogenation tended to select is chlorine, and it can recycle.Its reacted halogenide regained by flow process terminal also can re-use, but can be supplemented when having and reclaiming loss.Described thermal cracking process is using hydrogen as admixture, carry out heat of hydrogenation cracking and generate ethene, namely first hydrocracking chambers temp is risen between 500 DEG C to 1500 DEG C, the mol wt ratio that methyl halide mixes with hydrogen is between 1:1 to 1:500, the scope tending to select is between 1:10 to 1:100, hydrocracking room is entered after methine halide is mixed with the hydrogen of preheating, (hydrocracking process can be carried out in the halogenating reaction room of former the first step methane, enters in other reaction chamber and carry out after also methyl halide can being separated.Methyl halide can comprise a halogen, dihalo-, and three halogen and perhalogeno methane, do not need independent separation.), when hydrocracking room pressure is that 0.05 air is pressed onto between 5 normal atmosphere and carries out hydrocracking, the hydrocracking gas residence time in the reaction chamber, what tend to select was between 10 to 500 milliseconds between 5 milliseconds to 5000 milliseconds.Hydrocracking process can be carried out in the halogenating reaction room of former the first step methane, enters in other reaction chamber and carry out after also methyl halide can being separated.What hydrocracking temperatures tended to selection is between 800 DEG C to 1200 DEG C; What hydrocracking pressure tended to selection is between 0.1 to 1 normal atmosphere; The residence time in reaction chamber, what tend to selection was between 10 to 500 milliseconds between 5 milliseconds to 5000 milliseconds; Not consuming hydrogen and can reclaiming by prior art of single process outlet, can be recycled after being separated.Hydrogen halide is recycled by prior art.Partially halogenated methane is reduced into methane recovery and utilizes.The hydrocarbon polymer of high carbon number and comprise a small amount of halo height carbon number hydrocarbon polymer, carries out separating treatment by prior art, is output into product.
Chinese patent 200910117693.1 provides the process integration process of a kind of methane direct conversion ethene and synthetic gas, most basic petrochemical material can be obtained by methane---ethene, but transformation efficiency is not high, and the method exists, and temperature of reaction is high, methane conversion is low, manufacturing cost is high or flow process complicated, ethylene separation energy consumption is high, and flame condition is employed in reaction process, and in controlling the stable of reaction, and the resultant such as carbon distribution and tar is usually produced in reaction process, affect runoff yield to go out, need the shortcoming of frequent scale removal; If the resultant C of methane oxidation coupling can be made
2 +hydrocarbon is just further converted to other product without separation, a composite catalyst or multiple catalyzer reacts respectively continuously, then will break molecular balance, and greatly improve transformation efficiency, turn avoid the difficulty of the rare ethene of separation of oxygenated coupled product simultaneously.In follow-up conversion, the aromizing of alkene is also one and selects very well.Namely by aromizing, the alkene that methane oxidation coupling is produced is prepared into aromatic hydrocarbons, the chemical equilibrium of methane oxidation coupling can be broken.
Summary of the invention
The object of the present invention is to provide a kind of by containing methane feed through partially halogenated and partial oxidation synthesizing ethylene, ethene as the intermediate producing aromatic hydrocarbons, and then is converted into the process integration process of aromatic hydrocarbons with realizing methane high conversion.Use the present invention, petrochemical material---the aromatic hydrocarbons on basis can be obtained by methane, greatly improve the effective rate of utilization of methane.
The invention provides a kind of methane oxidation conversion is aromatics process, it is characterized in that this processing step is as follows:
1) enter containing methane feed in the fluidized-bed reactor that methane oxidation catalyst is housed and carry out oxidizing reaction; Or be divided into two portions containing methane feed, a part mix with chlorine and reacts in the halogenation reactor that methane halogenation catalyzer is housed, and reaction product contains with another part to enter in the fluidized-bed reactor that methane oxidation catalyst is housed together with methane feed again carries out oxidizing reaction; Reaction product in fluidized-bed reactor carries out gas solid separation, fluidized-bed reactor gaseous product enters step 2), the catalyst recirculation separated uses, in a fluidized bed reactor, containing methane feed through catalytic selective oxidation, methane is converted into ethene, ethane, CO, CO
2, H
2other oxygenatedchemicals of O, HCl and trace is as NO etc., and described methane halogenation catalyzer is by 10-60%Cr
2o
3, 0.5-10%Ce
2o
3and 30-89.5%Al
2o
3composition, with methane halogenation overall catalyst weight gauge;
2) come from step 1) fluidized-bed reactor gaseous product enter in the moving-burden bed reactor that aromatized catalyst is housed and carry out aromatization, ethene is further converted to aromatic hydrocarbons, moving-burden bed reactor reaction product carries out gas-liquid separation, gas (i.e. unreacted methane and other gas) returns step 1) in fluidized-bed reactor in continue reaction, product liquid enters aromatics seperation system, obtains different aromatic hydrocarbon product.
Described step 1) refer to pure methane, Sweet natural gas, coal-seam gas, biogas or associated gas containing methane feed.The reaction conditions of halogenation reactor is: normal pressure, 450-580 DEG C, and preferably at 520-560 DEG C, the volume proportion of methane and chlorine is 2:0.1 ~ 1, and the volume space velocity of methane is 1000 ~ 4000h
-1, preferred volume air speed is 1500-3500h
-1.
Described step 1) in methane oxidation catalyst be made up of 1.85-43% metal active constituent, 32-88.15% carrier and 10-25% binding agent, with overall catalyst weight gauge.Wherein the consisting of of metal active constituent: (a) sodium and/or lithium, content range is at 0.25-5.0; More than one of (b) calcium, magnesium and barium, content range is at 0.5-15.0%; C more than one of () vanadium, chromium and manganese, content range is at 1.0-20.0%:(d) lanthanum and/or cerium, content range is at 0.10-3.0%, and in metal active constituent, the content of each several part is with overall catalyst weight gauge.Described carrier is gama-alumina, kaolin or molecular sieve, and binding agent is alumina sol, silicon sol or amorphous aluminum silicate, is prepared into fluid catalyst by spray drying forming equipment.
Described step 1) in the reaction conditions of fluidized-bed reactor be: temperature of reaction 650 ~ 900 DEG C, best temperature of reaction is 660 ~ 720 DEG C, reaction pressure 0.1 ~ 1.0MPa, best reaction pressure 0.5 ~ 0.7MPa, air speed (volume space velocity) 10000 ~ 40000h
-1, be preferably 15000 ~ 25000h
-1, the mol ratio of methane and oxygen is 1.0 ~ 5.0, is preferably 3.0 ~ 4.5.
Described step 2) in the moving-bed aromatized catalyst mentioned be the moving-bed aromatized catalyst adopting ZSM-5, it consists of metal-modified ZSM-5 molecular sieve and carrier, and shape is spherical between 1.6-2.0 millimeter of diameter.The reaction conditions of moving-burden bed reactor is: temperature of reaction 340-550 DEG C, preferred 360-420 DEG C, pressure 0.02-0.8MPa, preferred 0.12-0.4MPa, and the weight hourly space velocity of ethene is 0.2-5h
-1, preferred 0.5-1.5h
-1; Reaction product enters aromatics seperation system, obtains the aromatic hydrocarbon product meeting target level of product quality.
The present invention compared with prior art tool has the following advantages:
1) methane is converted into ethene under lower temperature of reaction, can reduce the energy consumption in reaction process;
2) by unreacted methane freshening, thus make full use of methane, the hydro carbons such as propylene, butylene of generation also can be converted into aromatic hydrocarbons simultaneously, and the water that reaction generates can use as water coolant.Therefore, whole process is clean, almost do not have " three wastes " to discharge, and reaches the green production of cleaner production aromatic hydrocarbons;
3) eliminate the step of methane couple product cryogenic freezing separating ethene in process, the direct aromizing of the ethylene product that reaction is generated, generate the aromatic hydrocarbon product of high added value.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but do not limit use range of the present invention.
Accompanying drawing explanation
Fig. 1 is a kind of methane oxidation conversion of the present invention is the simple process flow diagram of aromatic hydrocarbons.
Reference numeral shown in figure is:
1, containing methane feed, 2, chlorine, 3, halogenation reactor, 4, halogenation reactor reaction product, 5, oxygen, 6, fluidized-bed reactor, 7, the built-in cyclonic separator of fluidized-bed reactor, 8, fluidized-bed reactor gaseous product, 9, moving-burden bed reactor, 10, moving-burden bed reactor reaction product, 11, gas-liquid separator, 12, product liquid, 13, aromatics seperation system, 14, benzene, 15, toluene, 16, dimethylbenzene, 17, gas.
Embodiment
As shown in Figure 1, two portions are divided into containing methane feed 1, a part enters separately after halogenation reactor 3 mixes with chlorine 2 carries out methane halogenation reaction, the reaction conditions of methane halogenation reaction is: normal pressure, 450-580 DEG C, preferably at 520-560 DEG C, the volume proportion of methane and chlorine is 2:0.1 ~ 1, and the volume space velocity of methane is 1000 ~ 4000h
-1, preferred volume air speed is 1500-3500h
-1.Halogenation reactor reaction product 4 carries out oxidizing reaction containing methane feed 1 and oxygen 5 with another road in fluidized-bed reactor 6, in fluidized-bed reactor 6, methane oxidation catalyst is housed, reaction conditions in fluidized-bed reactor 6 is: temperature of reaction 650 ~ 900 DEG C, best temperature of reaction is 660 ~ 720 DEG C, reaction pressure 0.1 ~ 1.0MPa, best reaction pressure 0.5 ~ 0.7MPa, air speed (volume space velocity) 10000 ~ 40000h
-1, be preferably 15000 ~ 25000h
-1, the mol ratio of methane and oxygen is 1.0 ~ 5.0, is preferably 3.0 ~ 4.5.In fluidized-bed reactor 6, methane is converted into ethene, ethane, CO, CO by a step
2, the product gas flow such as HCl, enter the built-in cyclonic separator 7 of fluidized-bed reactor and carry out gas solid separation, being separated the solid catalyst obtained falls to refluxing in fluidized bed reactor 6, the fluidized-bed reactor gaseous product 8 that separation obtains enters and is equipped with in the moving-burden bed reactor 9 of aromatized catalyst, the reaction conditions of moving-burden bed reactor is: temperature of reaction 340-550 DEG C, preferred 360-420 DEG C, pressure 0.02-0.8MPa, preferred 0.12-0.4MPa, the weight hourly space velocity of ethene is 0.2-5h
-1, preferred 0.5-1.5h
-1.In moving-burden bed reactor 9, the ethene of generation is made to be further converted to aromatic hydrocarbons, the moving-burden bed reactor reaction product 10 produced, after gas-liquid separator 11 is separated, gas 17 (i.e. unreacted methane and other gas) returns in the fluidized-bed reactor 6 of methane oxidation and reacts.Product liquid 12 enters aromatics seperation system 13 and is separated, and finally obtains aromatic hydrocarbon product, as benzene 14, toluene 15 and dimethylbenzene 16 etc.Adopt this technological process, methane conversion can reach 25% ~ 30 % by weight, and aromatics yield is 85% ~ 95 % by weight of methane conversion.
In the present invention, a part mixes with chlorine 2 containing methane feed 1, a certain amount of methyl chloride and methylene dichloride is produced in the halogenation reactor 3 that methane halogenation catalyzer is housed, it is as the initiator of methyl free radicals, mix containing methane feed 1 and oxygen 5 with another part, in the fluidized-bed reactor 6 that methane oxidation catalyst is housed, through catalytic selective oxidation, methane is converted into ethene, ethane, CO, CO
2, H
2other oxygenatedchemicals of O, HCl and trace; Here in halogenation reactor 3, methane halogenation catalyzer is housed, it consists of 10-60%Cr
2o
3, 0.5-10%Ce
2o
3and 30-89.5%Al
2o
3, prepare preformed catalyst by extrusion moulding.
Methane oxidation catalyst in described fluidized-bed reactor 6 is made up of 1.85-43% metal active constituent, 32-88.15% carrier and 10-25% binding agent, with methane oxidation catalyst total weight.Wherein the consisting of of metal active constituent: (a) sodium and/or lithium, content range is at 0.25-5.0%; More than one of (b) calcium, magnesium and barium, content range is at 0.5-15.0%; More than one of (c) vanadium, chromium and manganese, content range is at 1.0-20.0%; D () lanthanum and/or cerium, content range is at 0.10-3.0%, and in metal active constituent, the content of each several part is with methane oxidation catalyst total weight.Described carrier is gama-alumina, kaolin or molecular sieve; Binding agent is alumina sol, silicon sol or amorphous aluminum silicate, is prepared into fluid catalyst by spray drying forming equipment.
Described moving-bed aromatized catalyst is adopt the moving-bed aromatized catalyst of ZSM-5, and it consists of metal-modified ZSM-5 molecular sieve and carrier, and shape is spherical between 1.6-2.0 millimeter of diameter.
Claims (10)
1. methane oxidation conversion is a technique for aromatic hydrocarbons, it is characterized in that this technique comprises the steps:
1) enter containing methane feed in the fluidized-bed reactor that methane oxidation catalyst is housed and carry out oxidizing reaction; Or be divided into two portions containing methane feed, a part mix with chlorine and reacts in the halogenation reactor that methane halogenation catalyzer is housed, and reaction product contains with another part to enter in the fluidized-bed reactor that methane oxidation catalyst is housed together with methane feed again carries out oxidizing reaction; Reaction product in fluidized-bed reactor carries out gas solid separation, fluidized-bed reactor gaseous product enters step 2), the catalyst recirculation separated uses, in a fluidized bed reactor, be converted into containing ethylene streams containing methane feed, described methane halogenation catalyzer is by 10-60%Cr
2o
3, 0.5-10%Ce
2o
3and 30-89.5%Al
2o
3composition, with methane halogenation overall catalyst weight gauge;
2) come from step 1) fluidized-bed reactor gaseous product enter in the moving-burden bed reactor that aromatized catalyst is housed and carry out aromatization, ethene is further converted to aromatic hydrocarbons, moving-burden bed reactor reaction product carries out gas-liquid separation, gas returns step 1) in fluidized-bed reactor in continue reaction, product liquid enters aromatics seperation system, obtains different aromatic hydrocarbon product.
2. a kind of methane oxidation conversion according to claim 1 is the technique of aromatic hydrocarbons, it is characterized in that: described step 1) refer to pure methane, Sweet natural gas, coal-seam gas, biogas or associated gas containing methane feed.
3. a kind of methane oxidation conversion according to claim 1 is the technique of aromatic hydrocarbons, it is characterized in that: the reaction conditions of described halogenation reactor is: normal pressure, 450-580 DEG C, the volume proportion of methane and chlorine is 2:0.1 ~ 1, and the volume space velocity of methane is 1000 ~ 4000h
-1.
4. a kind of methane oxidation conversion according to claim 3 is the technique of aromatic hydrocarbons, it is characterized in that: the temperature of reaction of described halogenation reactor is at 520-560 DEG C, and the volume space velocity of methane is 1500-3500h
-1.
5. a kind of methane oxidation conversion according to claim 1 is the technique of aromatic hydrocarbons, it is characterized in that: described step 1) in methane oxidation catalyst be made up of 1.85-43% metal active constituent, 32-88.15% carrier and 10-25% binding agent, with overall catalyst weight gauge; Wherein the consisting of of metal active constituent: (a) sodium and/or lithium, content range is at 0.25-5.0%; More than one of (b) calcium, magnesium and barium, content range is at 0.5-15.0%; More than one of (c) vanadium, chromium and manganese, content range is at 1.0-20.0%; (d) lanthanum and/or cerium, content range is at 0.10-3.0%, and in metal active constituent, the content of each several part is with overall catalyst weight gauge; Described carrier is gama-alumina, kaolin or molecular sieve, and binding agent is alumina sol, silicon sol or amorphous aluminum silicate.
6. a kind of methane oxidation conversion according to claim 1 is the technique of aromatic hydrocarbons, it is characterized in that: described step 1) in the reaction conditions of fluidized-bed reactor be: temperature of reaction 650 ~ 900 DEG C, reaction pressure 0.1 ~ 1.0MPa, volume space velocity 10000 ~ 40000h
-1, the mol ratio of methane and oxygen is 1.0 ~ 5.0.
7. a kind of methane oxidation conversion according to claim 6 is the technique of aromatic hydrocarbons, it is characterized in that: described step 1) in the reaction conditions of fluidized-bed reactor be: temperature of reaction is 660 ~ 720 DEG C, reaction pressure 0.5 ~ 0.7MPa, volume space velocity 15000 ~ 25000h
-1, the mol ratio of methane and oxygen is 3.0 ~ 4.5.
8. a kind of methane oxidation conversion according to claim 1 is the technique of aromatic hydrocarbons, it is characterized in that: described step 2) in moving-bed aromatized catalyst be adopt the moving-bed aromatized catalyst of ZSM-5, it consists of metal-modified ZSM-5 molecular sieve and carrier, and shape is spherical between 1.6-2.0 millimeter of diameter.
9. a kind of methane oxidation conversion according to claim 1 is the technique of aromatic hydrocarbons, it is characterized in that: the reaction conditions of described moving-burden bed reactor is: temperature of reaction 340-550 DEG C, pressure 0.02-0.8MPa, and the weight hourly space velocity of ethene is 0.2-5h
-1.
10. a kind of methane oxidation conversion according to claim 9 is the technique of aromatic hydrocarbons, it is characterized in that: the reaction conditions of described moving-burden bed reactor is: temperature of reaction 360-420 DEG C, pressure 0.12-0.4MPa, and the weight hourly space velocity of ethene is 0.5-1.5h
-1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019164797A1 (en) * | 2018-02-20 | 2019-08-29 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
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| CN1280117A (en) * | 1999-07-13 | 2001-01-17 | 中国科学院力学研究所 | Methane converting process and apparatus for high efficiency production of ethylene |
| CN101456781A (en) * | 2009-01-08 | 2009-06-17 | 湖南大学 | Method for preparing aromatic hydrocarbons mixture |
| CN102093157A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Joint process for preparing ethylene and synthesis gas by direct conversion of methane |
-
2013
- 2013-11-07 CN CN201310556487.7A patent/CN104628511B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280117A (en) * | 1999-07-13 | 2001-01-17 | 中国科学院力学研究所 | Methane converting process and apparatus for high efficiency production of ethylene |
| CN101456781A (en) * | 2009-01-08 | 2009-06-17 | 湖南大学 | Method for preparing aromatic hydrocarbons mixture |
| CN102093157A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Joint process for preparing ethylene and synthesis gas by direct conversion of methane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019164797A1 (en) * | 2018-02-20 | 2019-08-29 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
| US11518722B2 (en) | 2018-02-20 | 2022-12-06 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
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