CN103864564A - Technique for processing methanol-to-propylene by-products - Google Patents
Technique for processing methanol-to-propylene by-products Download PDFInfo
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- CN103864564A CN103864564A CN201410062646.2A CN201410062646A CN103864564A CN 103864564 A CN103864564 A CN 103864564A CN 201410062646 A CN201410062646 A CN 201410062646A CN 103864564 A CN103864564 A CN 103864564A
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Abstract
The invention relates to a technique for processing methanol-to-propylene by-products. The technique is characterized by comprising the steps as follows: a liquid hydrocarbon by-product of methanol-to-propylene (MTP) is separated to obtain a dry gas, a liquefied gas and C5<+> non-aromatic and aromatic hydrocarbons after passing through two sections of fixed bed reactors of olefin aromatization and alkane aromatization; the dry gas and aromatic hydrocarbon are discharged out of a reaction system as products; the C5<+> non-aromatic hydrocarbon is returned to the alkane aromatization reactor to continue to react; the liquefied gas and the liquefied gas of the MTP process by-product enter the alkane aromatization reactor; a heat source required for aromatization of the liquefied gas is provided by a mode of adding methanol; the liquefied gas is converted into a mixed hydrocarbon product of taking aromatic hydrocarbon as a main component under the action of a molecular sieve based catalyst; and the mixed hydrocarbon product enters the dethanizer to separate after being processed by an oil-water separator. By adopting the process, gasoline aromatization and liquefied gas aromatization are combined, and the MTP by-product is effectively converted into the hydrocarbons. By adopting the process, the actual gaining rate of the liquid hydrocarbon by-product of the MTP can be up to 65-120%, and the hydrocarbon yield of liquid aromatization can be up to 32-40%.
Description
Technical field
The invention belongs to aromatic hydrocarbons chemical technology field, be specifically related to a kind of preparing propylene from methanol by product technological method for processing.
Background technology
Propylene is the second largest petrochemical industry basic material that is only second to ethene, and its maximum purposes is to produce polypropylene.Current more than 95% propylene is produced the byproduct of ethene and the byproduct of refinery FCC apparatus from steam cracking.But due to the unstable of world oil supply and the predicament of China's shortage petroleum resources, the source of developing the required important source material propylene of petrochemical complex is greatly limited.Exploitation through preparing propylene from methanol (MTP) technique, is not only conducive to realize the efficient utilization of coal by coal, can also alleviate the situation that state's inner propene is in short supply.Therefore, preparing propylene from methanol has obtained developing rapidly in China in recent years, and by the end of the year 2012, the coal-based propylene annual capacity of China has reached 1,360,000 tons, accounts for 7% left and right of China's propylene production capacity.
MTP technique, except production propylene product, is gone back a large amount of liquefied hydrocarbon (C of by-product
5 +) and liquefied gas.The liquefied hydrocarbon output of MTP technique large (be about propone output 40%), impurity few (without sulphur, without nitrogen), product component is mainly isoparaffin, alkene and aromatic hydrocarbons, there is very large appreciation potential, but current processing mode is to take out as blended gasoline component.The liquefaction tolerance of by-product is relatively few, and product component is mainly propane and butane, because output is relatively little, sells the scale that do not become.Along with developing rapidly of MTP technique, seek by product processing and utilization approach, to promote the value of by product extremely urgent.
Because the aromaticity content in MTP liquefied hydrocarbon by product is higher, therefore by it is carried out to catalytic reforming, be more rational processing scheme by the non-aromatic aromatic hydrocarbons that is converted into high added value wherein.In addition, by product liquefied gas also can be translated into aromatic hydrocarbons by the technology of aromizing.
CN1032697C discloses a kind of catalytic modification of poor quality gasoline-aromatization method, and the method Raw is introduced into first reactor, is 0.2～1.0h at 300～550 DEG C, 0.05～1.2MPa, mass space velocity
-1conditions of non-hydrogen under react, product after gas-liquid separation, C
5 +liquid obtains gasoline fraction by fractionation, is less than C
4gas after preheating, enter second stage reactor, at 480～650 DEG C, 0.05～1.5MPa, volume space velocity 20～2000h
-1condition under carry out aromatization, aromizing product, after gas-liquid separation, obtains being rich in gas and the aromatic hydrocarbons mixture of hydrogen.
CN101747933A has announced a kind of petroleum naphtha and light-hydrocarbon aromatized method for modifying, and the method is by petroleum naphtha and C
3～C
5lighter hydrocarbons under hydro condition, contact with aromatized catalyst and carry out aromatization modification reaction, the volume ratio of 250～600 DEG C, hydrogen and petroleum naphtha is 20～400.The method can be converted into stop bracket gasoline and high-quality liquefied gas by low-octane petroleum naphtha and low-carbon (LC) hydro carbons.
A kind of Pt/ZSM-5 of using catalyzer is disclosed in USP4835336 by C
6-C
12non-aromatic hydrocarbon is converted into the method for aromatic hydrocarbons, in order to improve arenes selectivity and to suppress hydrogenolysis, this catalyzer needs to carry out prevulcanized before use, although this technique has higher aromatics yield, but because adopting noble metal catalyst and needing prevulcanized, cause manufacturing cost higher.
The Cyclar technique (USP4642402) that British Petroleum Company p.l.c. (BP) and earth oil company (UOP) develop jointly, utilize low-molecular-weight alkane to carry out aromatization as propane and butane replace petroleum naphtha, the gasoline yield that is rich in aromatic hydrocarbons can reach 62～67%, but this technological reaction temperature is higher.
Current inferior patrol and liquefied gas complete processing, mainly for catalytic gasoline and low-carbon alkanes raw material, are not also reported for the complete processing of MTP by product.MTP by product character is special, and value-added space is large, and especially liquefied hydrocarbon by product, if adopt ZSM-5 molecular sieve catalyzer the non-aromatic hydrocarbon in liquefied hydrocarbon to be converted into the light aromatics of high added value, will bring considerable economic benefit for enterprise.Meanwhile, utilize liquefied gas through aromatization technology that the liquefied gas of by-product is also converted into aromatic hydrocarbons, just solved the marketing problem of liquefied gas simultaneously.But the Determination of Alkane Content of the liquefied gas of MTP by-product is higher, the liquefied gas through aromatization that is rich in alkane is violent thermo-negative reaction, in production process, need constantly to carry out concurrent heating, and aromatization of methanol reaction is very exothermic process, liquefied gas through aromatization and aromatization of methanol technology are coupled, can save the external heat source of aromatization process needs, thereby reduce system energy consumption.
Summary of the invention
The invention provides a kind of complete processing of MTP by product, two sections of aromatization of gas technology of this process using are by the non-aromatic aromatic hydrocarbons that is converted in liquefied hydrocarbon, utilize methyl alcohol and liquefied gas coupling aromatization technology that by product liquefied gas is also converted into aromatic hydrocarbons simultaneously, have advantages of that aromatics yield is high, energy consumption is low, economic benefit is rised in value large.
The present invention is a kind of preparing propylene from methanol by product technological method for processing, it is characterized in that:
By coal through the liquefied hydrocarbon by product of preparing propylene from methanol MTP technique after alkene aromizing and two sections of fixed-bed reactor of alkane aromatization, be isolated to dry gas, liquefied gas, C
5 +non-aromatic and aromatic hydrocarbons; Dry gas and aromatic hydrocarbons are discharged reaction system as product, C
5 +the non-aromatic alkane aromatization reaction device that returns continues reaction, together with the liquefied gas of liquefied gas and MTP technique by-product, enter aromatization reactor, provide liquefied gas through aromatization required thermal source by the mode of additional methyl alcohol, under molecular sieve catalyst effect, be converted into taking aromatic hydrocarbons as main hydrocarbon mixture product, hydrocarbon mixture product enters deethanizing column and separates after water-and-oil separator; This technique combines aromatization of gas, liquefied gas through aromatization technology, effectively MTP by product is converted into aromatic hydrocarbons; By this technique, the actual gaining rate of aromatic hydrocarbons of the liquefied hydrocarbon by product of MTP can reach 50～140%, and the aromatics yield of liquefied gas through aromatization can reach 30～45%;
MTP by product technological method for processing comprises the steps:
1) from the liquefied hydrocarbon by product of MTP technique after preheater is heated to temperature of reaction, enter in the fixed-bed reactor that molecular sieve catalyst is housed, be 0.1～2.0MPa at working pressure, temperature is 260～380 DEG C, and raw materials quality air speed is 0.5～8.0h
-1condition under carry out alkene aromatization; Catalyzer is the nano-ZSM-5 molecular sieve catalyzer after hydrothermal treatment consists modification, and the hydrothermal treatment consists temperature of ZSM-5 molecular sieve is 300～800 DEG C;
2) one section of alkene aromatization reaction products, after heating, enters in the alkane aromatization reaction device that metal-modified ZSM-5 molecular sieve catalyzer is housed, and is 0.1～2.0MPa at working pressure, and temperature of reaction is 380～520 DEG C, and raw materials quality air speed is 0.5～4.0h
-1condition under carry out the aromatization of alkane; Catalyzer is metal-modified nano-ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Zn, Ni, La, Mo, Cu, Fe, Mn, Cr, and the total charge capacity of metal is 0.5～8.0wt%;
3) reaction product of two sections of alkane aromatizations product after deethanizing column, debutanizing tower, Aromatics Extractive Project tower is divided into dry gas, liquefied gas, C
5 +non-aromatic and aromatic hydrocarbons;
4) step 3) separates the C obtaining
5 +non-aromaticly return to two sections of alkane aromatization reaction devices and continue reaction, liquefied gas product jointly enters in liquid gas aromatization reaction device and reacts with the liquefied gas by product of MTP technique; In liquid gas aromatization reaction device, pass into a certain amount of methyl alcohol through preheating, utilize the heat effect that methanol conversion produces directly to supplement liquefied gas through aromatization institute heat requirement; Reaction conditions is: 400～550 DEG C of temperature, and pressure 0.1～3.0MPa, the mol ratio of methyl alcohol and liquefied gas is 0.5:1～5:1, raw materials quality air speed is 0.5～5.0h
-1; Used catalyst is metal-modified ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Ga, Ni, Zn, Cu, Re, Sn, La, Tb, and metal total loading amount is 1.0～8.0wt%;
5) the hydrocarbon mixture component that liquefied gas through aromatization obtains enters deethanizing column and separates after water-and-oil separator.
According to MTP by product technological method for processing of the present invention, it is characterized in that:
After alkene aromizing and two sections of fixed-bed reactor of alkane aromatization, be isolated to dry gas, liquefied gas, C from the liquefied hydrocarbon by product of MTP technique
5 +non-aromatic and aromatic hydrocarbons; Dry gas and aromatic hydrocarbons are discharged reaction system as product, C
5 +the non-aromatic alkane aromatization reaction device that returns continues reaction, together with the liquefied gas of liquefied gas and MTP technique by-product, enter aromatization reactor, provide liquefied gas through aromatization required thermal source by the mode of additional methyl alcohol, under molecular sieve catalyst effect, be converted into taking aromatic hydrocarbons as main hydrocarbon mixture product, hydrocarbon mixture product enters deethanizing column and separates after water-and-oil separator; This technique combines aromatization of gas, liquefied gas through aromatization technology, effectively MTP by product is converted into aromatic hydrocarbons; By this technique, the actual gaining rate of aromatic hydrocarbons of the liquefied hydrocarbon by product of MTP can reach 65～120%, and the aromatics yield of liquefied gas through aromatization can reach 32～40%;
MTP by product technological method for processing comprises the steps:
1) from the liquefied hydrocarbon by product of MTP technique after preheater is heated to temperature of reaction, enter in the fixed-bed reactor that molecular sieve catalyst is housed, be 0.5～1.0MPa at working pressure, temperature is 280～340 DEG C, and raw materials quality air speed is 1.0～5.0h
-1condition under carry out alkene aromatization.Catalyzer is the nano-ZSM-5 molecular sieve catalyzer after hydrothermal treatment consists modification, and the hydrothermal treatment consists temperature of ZSM-5 molecular sieve is 450～650 DEG C;
2) one section of alkene aromatization reaction products, after heating, enters in the alkane aromatization reaction device that metal-modified ZSM-5 molecular sieve catalyzer is housed, and is 0.5～1.0MPa at working pressure, and temperature of reaction is 380～480 DEG C, and raw materials quality air speed is 1.0～3.0h
-1condition under carry out the aromatization of alkane.Catalyzer is metal-modified nano-ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Zn, Ni, La, Cr, and the total charge capacity of metal is 2.0～6.0wt%;
3) reaction product of two sections of alkane aromatizations product after deethanizing column, debutanizing tower, Aromatics Extractive Project tower is divided into dry gas, liquefied gas, C
5 +non-aromatic and aromatic hydrocarbons;
4) step 3) separates the C obtaining
5 +non-aromaticly return to two sections of alkane aromatization reaction devices and continue reaction, liquefied gas product jointly enters in liquid gas aromatization reaction device and reacts with the liquefied gas by product of MTP technique.In liquid gas aromatization reaction device, pass into a certain amount of methyl alcohol through preheating, utilize the heat effect that methanol conversion produces directly to supplement liquefied gas through aromatization institute heat requirement.Reaction conditions is: 440～520 DEG C of temperature, and pressure 0.5～2.0MPa, the mol ratio of methyl alcohol and liquefied gas is 1:1～3:1, raw materials quality air speed is 0.5～3.0h
-1.Used catalyst is metal-modified ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Ga, Ni, Zn, Sn, La, and metal total loading amount is 2.0～6.0wt%;
5) the hydrocarbon mixture component that liquefied gas through aromatization obtains enters deethanizing column and separates after water-and-oil separator.
The present invention has following advantage: (1) adopts alkene aromizing and alkane aromatization technology by the non-aromatic aromatic hydrocarbons that is at utmost converted in liquefied hydrocarbon, and the unreacted non-aromatic alkane aromatization reaction device that returns, has higher aromatics yield; (2) liquefied gas this technique being produced and the liquefied gas by product of MTP technique carry out aromizing jointly, utilize the heat release of aromatization of methanol to supplement the heat absorption of liquefied gas through aromatization, and system energy consumption is lower.
Brief description of the drawings
Fig. 1 is MTP by product technological method for processing schematic flow sheet provided by the invention.In figure: 1-raw materials furnace and heating; 2-alkene aromatization reactor; 3-alkene aromizing product process furnace; 4-alkane aromatization reaction device; 5-deethanizing column; 6-debutanizing tower; 7-Aromatics Extractive Project tower; 8-liquid gas aromatization reaction device; 9-water-and-oil separator; 10-methanol preheater.
Embodiment
In order to further illustrate MTP by product complete processing of the present invention, below in conjunction with accompanying drawing, process of the present invention is described.
As shown in Figure 1, MTP liquefied hydrocarbon by product enters alkene aromatization reactor 2 and reacts after process furnace 1 is heated to temperature of reaction, and reaction product enters alkane aromatization reaction device 4 again and carries out alkane aromatization reaction after process furnace 3 heating.Alkane aromatization reaction product obtains dry gas, liquefied gas, C after deethanizing column 5, debutanizing tower 6 separate with Aromatics Extractive Project tower 7
5 +non-aromatic and aromatic hydrocarbons.Dry gas and aromatic hydrocarbons are discharged system as product, C
5 +the non-aromatic alkane aromatization reaction device 4 that returns is proceeded reaction, the liquefied gas by product of liquefied gas and MTP technique jointly enters liquid gas aromatization reaction device 8 and reacts, in aromatization reactor 8, pass into a certain amount of methyl alcohol through preheater 10 preheatings, product returns to deethanizing column 5 and separates after water-and-oil separator 9.
Embodiment 1
(1) MTP liquefied hydrocarbon by product aromizing
First MTP technique liquefied hydrocarbon by product enters one section of alkene aromatization reactor, and catalyzer is the nano-ZSM-5 molecular sieve through 450 DEG C of hydrothermal treatment consists modifications, is 280 DEG C in temperature of reaction, and pressure is 0.5MPa, and mass space velocity is 1.0h
-1condition under react.Then enter two sections of alkane aromatization reaction devices, catalyzer is the ZSM-5 molecular sieve catalyzer of Zn, Ni modification, and wherein the charge capacity of ZnO is 2.0wt%, and the charge capacity of NiO is 1.0wt%.Reaction conditions is that temperature is 380 DEG C, and pressure is 0.5MPa, and mass space velocity is 1.0h
-1.MTP liquefied hydrocarbon by product feedstock property is as shown in table 1, and reaction result is as shown in table 2.
(2) MTP liquefied gas by product aromizing
Adopting MTP liquefied gas by product and methyl alcohol is raw material, and liquefied gas feedstock property is as shown in table 3.After liquefied gas and methanol mixed, enter fixed-bed reactor, catalyzer adopts the ZSM-5 molecular sieve catalyzer of Zn modification, and wherein the charge capacity of ZnO is 2.0wt%.Be 440 DEG C in temperature of reaction, pressure is 0.5MPa, and the mol ratio of methyl alcohol and liquefied gas is 1:1, and raw materials quality air speed is 0.5h
-1condition under react, reaction result is as shown in table 4.
Embodiment 2
(1) MTP liquefied hydrocarbon by product aromizing
First MTP technique liquefied hydrocarbon by product enters one section of alkene aromatization reactor, and catalyzer is the nano-ZSM-5 molecular sieve through 550 DEG C of hydrothermal treatment consists modifications, is 300 DEG C in temperature of reaction, and pressure is 1.0MPa, and mass space velocity is 2.0h
-1condition under react.Then enter two sections of alkane aromatization reaction devices, catalyzer is the ZSM-5 molecular sieve catalyzer of Zn, Ni, La modification, and the charge capacity of ZnO is 2.0wt%, and the charge capacity of NiO is 1.0wt%, La
2o
3charge capacity be 1.0wt%.Reaction conditions is that temperature is 420 DEG C, and pressure is 1.0MPa, and mass space velocity is 1.0h
-1, reaction result is as shown in table 2.
(2) MTP liquefied gas by product aromizing
Adopting MTP liquefied gas by product and methyl alcohol is raw material, and liquefied gas feedstock property is as shown in table 3.After liquefied gas and methanol mixed, enter fixed-bed reactor, catalyzer adopts the composite modified ZSM-5 molecular sieve catalyzer of Ga, Ni, Ga
2o
3charge capacity be 0.5wt%, the charge capacity of NiO is 3.5wt%.Be 460 DEG C in temperature of reaction, pressure is 1.0MPa, and the mol ratio of methyl alcohol and liquefied gas is 2:1, and raw materials quality air speed is 1.5h
-1condition under react, reaction result is as shown in table 4.
Embodiment 3
(1) MTP liquefied hydrocarbon by product aromizing
First MTP technique liquefied hydrocarbon by product enters one section of alkene aromatization reactor, and catalyzer is the nano-ZSM-5 molecular sieve through 600 DEG C of hydrothermal treatment consists modifications, is 340 DEG C in temperature of reaction, and pressure is 0.5MPa, and mass space velocity is 4.0h
-1condition under react.Then enter two sections of alkane aromatization reaction devices, catalyzer is the ZSM-5 molecular sieve catalyzer of Zn, Cr modification, and the charge capacity of ZnO is 2.0wt%, Cr
2o
3charge capacity be 3.0wt%.Reaction conditions is that temperature is 450 DEG C, and pressure is 0.5MPa, and mass space velocity is 3.0h
-1, reaction result is as shown in table 2.
(2) MTP liquefied gas by product aromizing
Adopting MTP liquefied gas by product and methyl alcohol is raw material, and liquefied gas feedstock property is as shown in table 3.After liquefied gas and methanol mixed, enter fixed-bed reactor, catalyzer adopts Ga, Ni, the composite modified ZSM-5 molecular sieve catalyzer of Sn, wherein Ga
2o
3charge capacity be 1.5wt%, the charge capacity of NiO is 4wt%, the charge capacity of Sn is 0.5wt%, is 480 DEG C in temperature of reaction, pressure is 2.0MPa, the mol ratio of methyl alcohol and liquefied gas is 2:1, raw materials quality air speed is 2.0h
-1condition under react, reaction result is as shown in table 4.
Embodiment 4
(1) MTP liquefied hydrocarbon by product aromizing
First MTP technique liquefied hydrocarbon by product enters one section of alkene aromatization reactor, and catalyzer is the nano-ZSM-5 molecular sieve through 650 DEG C of hydrothermal treatment consists modifications, is 340 DEG C in temperature of reaction, and pressure is 1.0MPa, and mass space velocity is 3.0h
-1condition under react.Then enter two sections of alkane aromatization reaction devices, catalyzer is the ZSM-5 molecular sieve catalyzer of Ni, La modification, and the charge capacity of NiO is 3.0wt%, La
2o
3charge capacity is 1.0wt%, and reaction conditions is that temperature is 480 DEG C, and pressure is 1.0MPa, and mass space velocity is 3.0h
-1, reaction result is as shown in table 2.
(2) MTP liquefied gas by product aromizing
Adopting MTP liquefied gas by product and methyl alcohol is raw material, and liquefied gas feedstock property is as shown in table 3.After liquefied gas and methanol mixed, enter fixed-bed reactor, catalyzer adopts the composite modified ZSM-5 molecular sieve catalyzer of Zn, Sn, and wherein the charge capacity of ZnO is 4.5wt%, SnO
2charge capacity be 0.5wt%.Be 520 DEG C in temperature of reaction, pressure is 2.0MPa, and the mol ratio of methyl alcohol and liquefied gas is 3:1, and raw materials quality air speed is 3.0h
-1condition under react, reaction result is as shown in table 4.
Table 1MTP liquefied hydrocarbon by product PONA composition
| Carbon number | Normal paraffin | Isoparaffin | Alkene | Naphthenic hydrocarbon | Aromatic hydrocarbons | Amount to |
| 4.00 | 0.00 | 0.01 | 0.09 | 0.00 | 0.00 | 0.10 |
| 5.00 | 1.63 | 13.81 | 6.36 | 1.18 | 0.00 | 22.98 |
| 6.00 | 0.50 | 6.69 | 6.43 | 6.47 | 0.29 | 20.38 |
| 7.00 | 1.36 | 0.94 | 8.41 | 3.00 | 4.61 | 18.32 |
| 8.00 | 0.34 | 2.91 | 4.96 | 1.48 | 19.08 | 28.77 |
| 9.00 | 0.00 | 0.46 | 0.78 | 0.40 | 7.19 | 8.83 |
| 10.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.55 | 0.55 |
| 11.00 | 0.00 | 0.07 | 0.00 | 0.00 | 0.00 | 0.07 |
| Add up to | 3.83 | 24.89 | 27.03 | 12.53 | 31.72 | 99.99 |
Two sections of aromatization results of table 2 embodiment 1～4MTP liquefied hydrocarbon by product
Note: aromatics yield=liquid yield arenes selectivity; Aromaticity content in the actual gaining rate of aromatic hydrocarbons=(aromaticity content in liquid yield arenes selectivity-raw material)/raw material.
Table 3MTP liquefied gas by product composition
| Component | Propane | Propylene | Trimethylmethane | Normal butane | Just, iso-butylene | Trans-2-butene | Cis-2-butene | C5+ |
| Content wt% | 17.10 | 0.23 | 39.31 | 10.91 | 19.52 | 6.84 | 4.25 | 1.84 |
Table 4 embodiment 1～4 liquefied gas and aromatization of methanol reaction result
Claims (2)
1. a preparing propylene from methanol by product technological method for processing, is characterized in that:
By coal through the liquefied hydrocarbon by product of preparing propylene from methanol MTP technique after alkene aromizing and two sections of fixed-bed reactor of alkane aromatization, be isolated to dry gas, liquefied gas, C
5 +non-aromatic and aromatic hydrocarbons; Dry gas and aromatic hydrocarbons are discharged reaction system as product, C
5 +the non-aromatic alkane aromatization reaction device that returns continues reaction, together with the liquefied gas of liquefied gas and MTP technique by-product, enter aromatization reactor, provide liquefied gas through aromatization required thermal source by the mode of additional methyl alcohol, under molecular sieve catalyst effect, be converted into taking aromatic hydrocarbons as main hydrocarbon mixture product, hydrocarbon mixture product enters deethanizing column and separates after water-and-oil separator; This technique combines aromatization of gas, liquefied gas through aromatization technology, effectively MTP by product is converted into aromatic hydrocarbons; By this technique, the actual gaining rate of aromatic hydrocarbons of the liquefied hydrocarbon by product of MTP reaches 50～140%, and the aromatics yield of liquefied gas through aromatization reaches 30～45%;
MTP by product technological method for processing comprises the steps:
1) from the liquefied hydrocarbon by product of MTP technique after preheater is heated to temperature of reaction, enter in the fixed-bed reactor that molecular sieve catalyst is housed, be 0.1～2.0MPa at working pressure, temperature is 260～380 DEG C, and raw materials quality air speed is 0.5～8.0h
-1condition under carry out alkene aromatization; Catalyzer is the nano-ZSM-5 molecular sieve catalyzer after hydrothermal treatment consists modification, and the hydrothermal treatment consists temperature of ZSM-5 molecular sieve is 300～800 DEG C;
2) one section of alkene aromatization reaction products, after heating, enters in the alkane aromatization reaction device that metal-modified ZSM-5 molecular sieve catalyzer is housed, and is 0.1～2.0MPa at working pressure, and temperature of reaction is 380～520 DEG C, and raw materials quality air speed is 0.5～4.0h
-1condition under carry out the aromatization of alkane; Catalyzer is metal-modified nano-ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Zn, Ni, La, Mo, Cu, Fe, Mn, Cr, and the total charge capacity of metal is 0.5～8.0wt%;
3) reaction product of two sections of alkane aromatizations product after deethanizing column, debutanizing tower, Aromatics Extractive Project tower is divided into dry gas, liquefied gas, C
5 +non-aromatic and aromatic hydrocarbons;
4) step 3) separates the C obtaining
5 +non-aromaticly return to two sections of alkane aromatization reaction devices and continue reaction, liquefied gas product jointly enters in liquid gas aromatization reaction device and reacts with the liquefied gas by product of MTP technique; In liquid gas aromatization reaction device, pass into a certain amount of methyl alcohol through preheating, utilize the heat effect that methanol conversion produces directly to supplement liquefied gas through aromatization institute heat requirement; Reaction conditions is: 400～550 DEG C of temperature, and pressure 0.1～3.0MPa, the mol ratio of methyl alcohol and liquefied gas is 0.5:1～5:1, raw materials quality air speed is 0.5～5.0h
-1; Used catalyst is metal-modified ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Ga, Ni, Zn, Cu, Re, Sn, La, Tb, and metal total loading amount is 1.0～8.0wt%;
5) the hydrocarbon mixture component that liquefied gas through aromatization obtains enters deethanizing column and separates after water-and-oil separator.
2. according to MTP by product technological method for processing claimed in claim 1, it is characterized in that:
After alkene aromizing and two sections of fixed-bed reactor of alkane aromatization, be isolated to dry gas, liquefied gas, C from the liquefied hydrocarbon by product of MTP technique
5 +non-aromatic and aromatic hydrocarbons; Dry gas and aromatic hydrocarbons are discharged reaction system as product, C
5 +the non-aromatic alkane aromatization reaction device that returns continues reaction, together with the liquefied gas of liquefied gas and MTP technique by-product, enter aromatization reactor, provide liquefied gas through aromatization required thermal source by the mode of additional methyl alcohol, under molecular sieve catalyst effect, be converted into taking aromatic hydrocarbons as main hydrocarbon mixture product, hydrocarbon mixture product enters deethanizing column and separates after water-and-oil separator; This technique combines aromatization of gas, liquefied gas through aromatization technology, effectively MTP by product is converted into aromatic hydrocarbons; By this technique, the actual gaining rate of aromatic hydrocarbons of the liquefied hydrocarbon by product of MTP reaches 65～120%, and the aromatics yield of liquefied gas through aromatization reaches 32～40%;
MTP by product technological method for processing comprises the steps:
1) from the liquefied hydrocarbon by product of MTP technique after preheater is heated to temperature of reaction, enter in the fixed-bed reactor that molecular sieve catalyst is housed, be 0.5～1.0MPa at working pressure, temperature is 280～340 DEG C, and raw materials quality air speed is 1.0～5.0h
-1condition under carry out alkene aromatization; Catalyzer is the nano-ZSM-5 molecular sieve catalyzer after hydrothermal treatment consists modification, and the hydrothermal treatment consists temperature of ZSM-5 molecular sieve is 450～650 DEG C;
2) one section of alkene aromatization reaction products, after heating, enters in the alkane aromatization reaction device that metal-modified ZSM-5 molecular sieve catalyzer is housed, and is 0.5～1.0MPa at working pressure, and temperature of reaction is 380～480 DEG C, and raw materials quality air speed is 1.0～3.0h
-1condition under carry out the aromatization of alkane; Catalyzer is metal-modified nano-ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Zn, Ni, La, Cr, and the total charge capacity of metal is 2.0～6.0wt%;
3) reaction product of two sections of alkane aromatizations product after deethanizing column, debutanizing tower, Aromatics Extractive Project tower is divided into dry gas, liquefied gas, C
5 +non-aromatic and aromatic hydrocarbons;
4) step 3) separates the C obtaining
5 +non-aromaticly return to two sections of alkane aromatization reaction devices and continue reaction, liquefied gas product jointly enters in liquid gas aromatization reaction device and reacts with the liquefied gas by product of MTP technique; In liquid gas aromatization reaction device, pass into a certain amount of methyl alcohol through preheating, utilize the heat effect that methanol conversion produces directly to supplement liquefied gas through aromatization institute heat requirement; Reaction conditions is: 440～520 DEG C of temperature, and pressure 0.5～2.0MPa, the mol ratio of methyl alcohol and liquefied gas is 1:1～3:1, raw materials quality air speed is 0.5～3.0h
-1; Used catalyst is metal-modified ZSM-5 molecular sieve catalyzer, and modified metal is one or more in Ga, Ni, Zn, Sn, La, and metal total loading amount is 2.0～6.0wt%;
5) the hydrocarbon mixture component that liquefied gas through aromatization obtains enters deethanizing column and separates after water-and-oil separator.
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| CN104355960A (en) * | 2014-11-11 | 2015-02-18 | 中国海洋石油总公司 | Method for preparing propylene and BTX by using methyl alcohol |
| CN107879870A (en) * | 2017-11-29 | 2018-04-06 | 神华集团有限责任公司 | The separator and method of C9 cuts in process of preparing propylene from coal-based methanol accessory substance |
| CN112322343A (en) * | 2020-10-10 | 2021-02-05 | 国家能源集团宁夏煤业有限责任公司 | Method and device for producing high-aromatic-content gasoline by MTP byproduct mixed aromatic hydrocarbon modification, high-aromatic-content gasoline and application thereof |
| CN116162073A (en) * | 2022-12-31 | 2023-05-26 | 中海油天津化工研究设计院有限公司 | Combined process for preparing propylene oxide from Fischer-Tropsch fraction oil |
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| CN103418426A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Binder-free methanol-to-aromatic hydrocarbon catalyst and preparation method thereof |
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| US20100160700A1 (en) * | 2008-12-18 | 2010-06-24 | Chevron U.S.A. Inc. | Process and catalysts for reforming fisher tropsch naphthas to aromatics |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355960A (en) * | 2014-11-11 | 2015-02-18 | 中国海洋石油总公司 | Method for preparing propylene and BTX by using methyl alcohol |
| CN107879870A (en) * | 2017-11-29 | 2018-04-06 | 神华集团有限责任公司 | The separator and method of C9 cuts in process of preparing propylene from coal-based methanol accessory substance |
| CN107879870B (en) * | 2017-11-29 | 2023-10-20 | 神华集团有限责任公司 | Separation device and method for C9 fraction in byproduct of coal-based methanol-to-propylene process |
| CN112322343A (en) * | 2020-10-10 | 2021-02-05 | 国家能源集团宁夏煤业有限责任公司 | Method and device for producing high-aromatic-content gasoline by MTP byproduct mixed aromatic hydrocarbon modification, high-aromatic-content gasoline and application thereof |
| CN116162073A (en) * | 2022-12-31 | 2023-05-26 | 中海油天津化工研究设计院有限公司 | Combined process for preparing propylene oxide from Fischer-Tropsch fraction oil |
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