CN106278793A - A kind of moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen and combination unit - Google Patents
A kind of moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen and combination unit Download PDFInfo
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
The invention provides a kind of moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen and combination unit, the method, using modified ZSM 5 is catalyst, two sections of fixed bed reactors, operation pressure is 0.1～5.0Mpa, and operation temperature is 300 460 DEG C, and raw material liq air speed is 0.1～6.0h‑1Under the conditions of methanol oxidation be converted into the product based on aromatic hydrocarbons, operating condition easily reaches.Wherein, second segment reactor primarily serves the purpose of non-aromatics and the lower carbon number hydrocarbons aromatisation again that first paragraph reactor produces, and oil phase productivity is more than 40%, and wherein arene content is more than 80%, has total arenes selectivity high, technological operation advantage flexibly.Meanwhile, the yield again with raising target product aromatic hydrocarbons and the selectivity of by-product, and by-product hydrogen can be passed through, and device achieves continuous prodution.
Description
Technical field
The present invention relates to technical field of petrochemical industry, in particular to a kind of moving bed methanol aromatic hydrocarbons and coproduct hydrogen
Method and combination unit.
Background technology
Low-carbon (LC) aromatic hydrocarbons mainly includes benzene,toluene,xylene, is typically called for short BTX, is important basic chemical industry raw material, wherein
Xylol (PX) accounts for about the 45% of BTX total quantity consumed.Industrial aromatics production about about 95% comes from petrochemical industry, few
Amount is from coal tar processing.China's BTX yield about 14,200,000 tons in 2010, Apparent con-sumption reaches 19,000,000 tons, and insufficiency of supply-demand is about
4800000 tons, the wherein PX degree of self-sufficiency only 61.6%, net importation 3,320,000 tons.In order to fill up the breach in aromatic hydrocarbons market, reduce aromatic hydrocarbons pair
The dependence of petroleum resources, from resourceful coal resources conversion for preparing arene, is possible not only to alleviate the shortage of aromatic hydrocarbon resource, improves
The added value of coal downstream product, extends Chemical Industry chain, has important value.In view of the virtue that current China is growing
The problems such as the coal-based methanol of hydrocarbon demand and day by day production capacity surplus, the exploitation actively developing coal-based methanol aromatic hydrocarbons technology is not only alleviated
The market demand to low-carbon (LC) aromatic hydrocarbons, the also comprehensive utilization for coal-based methanol have found an attainable road.According to country
The Committee of Development and Reform discloses in " planning of coal deep processing demonstrative project ", and coal aromatic hydrocarbons has been put into Coal Chemical Industry demonstration coming years emphasis
One of direction.
Methanol aromatic hydrocarbons theory occurs in the MTG technology of Mobil company exploitation the earliest, and 20 century 70 Mobil are public
Department develops ZSM-5 zeolite molecular sieve, utilizes this zeolite molecular sieve can effectively convert methanol into high-knock rating gasoline, its
Middle arene content is more than 35%.Subsequently Mobil company at U. S. application patent USP4590321, disclose methanol aromatic hydrocarbons
Experimental result, ZSM-5 molecular sieve catalyst ratio on higher hydrocarbon, the selectivity of aromatic hydrocarbons modified for experimental result display P is unmodified
ZSM-5 molecular sieve well a lot, but arene content is not the highest.Subsequently, Mobil company has applied for again United States Patent (USP)
USP4686312, discloses the multistage reaction process that the low-carbon oxygen-containing compounds such as methanol are converted into the product rich in aromatic hydrocarbons.?
First paragraph methanol is converted into low-carbon alkanes and alkene, subsequently enters second segment reactor, sends out further under the effect of catalyst
Raw aromatization, it is thus achieved that rich in the product of low-carbon (LC) aromatic hydrocarbons.
At present, domestic have a lot of scientific research institution all in exploitation MTA catalysis and Technology, wherein Chinese Academy of Sciences Shanxi coalification
The fixed bed methanol aromatic hydrocarbons technology cooperated with Sai Ding engineering company, the recirculating fluidized bed methanol aromatic hydrocarbons of Tsing-Hua University
(FMTA) technology is all being actively pushed forward the pilot scale stage, and Henan coalification group academy and Beijing University of Chemical Technology are also in cooperation development first
Alcohol aromatic hydrocarbons technology.Shanxi coalification patent CN1880288A disclose a kind of process of methanol conversion for preparing arene and catalyst and
Method for preparing catalyst.Tsing-Hua University's patent CN101244969A discloses the dress of a kind of continuous aromatization and catalyst regeneration
Putting and method, belong to field of chemical equipment, use fluidization to convert methanol into aromatic hydrocarbons, the present invention has and can urge by modulation
Agent activity and selectivity, can make reaction continuous operation and not parking.But this patent is without reference to the profit of byproduct of reaction
With, the selectivity of overall aromatics is the highest.Tianji Coal Chemical Industry Group Co., Ltd.'s patent CN101550051A discloses one
Kind improve the selective technique of aromatization of methanol preparing aromatic hydrocarbon and the preparation method of catalyst thereof, this patent with methanol as raw material,
With the Ga of variable concentrations, Zn, Cu, Ag isoreactivity ion composite modified HZSM-5 molecular sieve catalyst, catalysis methanol aromatisation is anti-
Should, using fixed bed continuity method or suspension bed continuity method, reaction pressure is 0.1～3.5Mpa, and reaction temperature 380～500 DEG C are former
Feed liquid body air speed is 0.1～10.0h-.China National Offshore Oil Corporation's patent CN101602646A discloses a kind of methanol/diformazan
Ether produces method and the special reaction device thereof of aromatic hydrocarbons, and described reaction unit is the fluid bed of successive reaction regeneration.
It is first that CN101823929A discloses a kind of methanol or the system of dimethyl ether conversion preparing aromatic hydrocarbon and technique, material benzenemethanol or dimethyl ether
First reacting in aromatization reactor, reacted product is hydrogen after separating, methane, mixes C8Aromatic hydrocarbons and part C9 +
Aromatic hydrocarbons is as output of products, and C2 +Non-aromatics and except mixing C8Aromatic hydrocarbons and part C9 +Aromatic hydrocarbons outside aromatic hydrocarbons is then as recycle
Stream returns the further aromatization of corresponding reactor.
At present, the research emphasis of aromatization of methanol reaction is mainly in improvement and the type of reactor of catalyst.Wherein, Shanxi
Coalification Tsing-Hua University in one's power has carried out the simple research of simple separation and cycling and reutilization to the product of aromatization of methanol, does not still have
There are the product separation of aromatization of methanol course of reaction and the report of the problem that recycles of lower carbon number hydrocarbons, are suitable for industrialized methanol virtue
There is not been reported for the method and device of structure.
In view of this, the special proposition present invention.
Summary of the invention
The first object of the present invention is to provide a kind of moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen, to overcome methanol
The defect made a low multiple use of by-product in aromatization process, described moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen are adopted
With the ZSM-5 catalyst modified with Zn, P, Ag, Ga, methanol conversion more than 80%, in product arene content 50～
60wt%, has total arenes selectivity high, technological operation advantage flexibly.
The second object of the present invention is to provide a kind of described a kind of moving bed methanol aromatic hydrocarbons and the combination of coproduct hydrogen
Device, this combination unit overcomes in prior art and can not the product of aromatization of methanol course of reaction separate and the circulation of lower carbon number hydrocarbons
Utilizing question, by the yield again with raising target product aromatic hydrocarbons and the selectivity of by-product, and by-product hydrogen, and fill
Put and achieve continuous prodution.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen, comprise the following steps:
1) methanol carries out aromatization, and product enters step 2)；
2) from step 1) product enter three phase separation unit carry out isolated gas, oil-phase product and water；
Oil-phase product enters step 3), gas enters step 4)；
3) to from step 2) oil-phase product carry out Aromatics Extractive Project, oil-phase product is separated into non-aromatics and low-carbon (LC) mixing
Aromatic hydrocarbons, non-aromatics enters step 5 after raffinating oil), mixing aromatic hydrocarbons enters step 6)；
4) to from step 2) and step 4) gaseous product separate, obtain dry gas and liquefied gas, dry gas by become
Pressure absorption enters step 5 as fuel gas, liquefied gas after reclaiming hydrogen)；
5) to from step 4) liquefied gas and step 3) non-aromatics product carry out aromatic hydrocarbons structureization reaction, reaction generate
Gaseous product enters step 4), oil-phase product enters Aromatics Extractive Project and enters step 3)；
6) to from step 3) low-carbon (LC) mixing aromatic hydrocarbons enter aromatic hydrocarbons rectification cell, isolate BTX and C9 +Aromatic hydrocarbons.
Preferably, the condition of described aromatization is air speed 0.1～3.0h-1, temperature 380～450 DEG C and pressure 0.1-
2.0MPa。
Preferably, the catalyst used by described aromatization is the ZSM-5 catalyst that Zn, P, Ag and Ga are modified, its
In, the silica alumina ratio of ZSM-5 catalyst is 36～100.
The application selects and uses modified ZSM-5 is catalyst, two sections of fixed bed reactors, operation pressure be 0.1～
5.0Mpa, operation temperature is 300-460 DEG C, and raw material liq air speed is 0.1～6.0h-1Under the conditions of methanol oxidation be converted into aromatic hydrocarbons
Being main product, operating condition easily reaches.The second segment reactor of the application primarily serves the purpose of what first paragraph reactor produced
Non-aromatics and lower carbon number hydrocarbons aromatisation again, oil phase productivity is more than 40%, and wherein arene content is more than 80%.The present invention has always
Arenes selectivity is high, technological operation advantage flexibly.
Wherein, BTX is called for short light aromatics, the mixture of benzene-toluene mixture.
Preferably, in step 1) in, it is moving-burden bed reactor that described methanol carries out the reactor of aromatization.
Preferably, in step 1) in, in the ZSM-5 catalyst that described Zn, P, Ag, Ga are modified, modifying element Zn accounts for catalysis
The 1%～6% of agent gross weight, preferred 2%～4%；
P accounts for the 2%～10% of total catalyst weight, preferred 3%～6%；
Ag accounts for the 1%～4% of total catalyst weight, preferred 2%～3%；
Ga accounts for the 0.5%～5% of total catalyst weight, preferred 2%～4%；
In the ZSM-5 catalyst that further preferred described Zn, P, Ag, Ga is modified, modified metal element is with Zn-P, Zn-P-
The mode of Ag or Ga-P combines.
The ratio of above-mentioned modifying element and compound mode, catalytic effect is more preferable.
Preferably, in step 5) in, the reactor of described aromatization is fixed bed or moving-burden bed reactor.
Preferably, in step 5) in, the condition of described aromatic hydrocarbons structureization reaction is reaction temperature 450-550 DEG C, Feed space velocities
It is 0.5～1.0h-1With pressure 0.2-0.8Mpa.
Preferably, in step 5) in, in the HZSM-5 molecular sieve catalyst that described Zn is modified, modifying element Zn accounts for catalyst
The 1%～8% of gross weight, preferred 2%～5%.
Moving bed methanol aromatic hydrocarbons as above and the combination unit of coproduct hydrogen, including aromatization of methanol unit, three-phase
Separative element, gas separation unit, Aromatics Extractive Project unit, aromatic hydrocarbons rectification cell and aromatization of low carbon hydrocarbon unit；
Wherein, the outlet of described aromatization of methanol unit connects with described three phase separation unit entrance, described three phase separation list
The gaseous phase outlet of unit connects with described gas separation unit and described Aromatics Extractive Project unit respectively with oil phase outlet, and described gas divides
Liquefied gas from unit exports and connects with the entrance of described aromatization of low carbon hydrocarbon unit, the gas phase of described aromatization of low carbon hydrocarbon unit
Outlet connects with the entrance of described gas separation unit, oil phase outlet and the described Aromatics Extractive Project of described aromatization of low carbon hydrocarbon unit
The entrance of unit is connected, the non-aromatics outlet of described Aromatics Extractive Project unit and the entrance phase of described aromatization of low carbon hydrocarbon unit
Even, the aromatic hydrocarbons outlet of described Aromatics Extractive Project unit connects with described aromatic hydrocarbons rectification cell.
Compared with prior art, the invention have the benefit that
1), moving bed methanol aromatic hydrocarbons provided herein and the method for coproduct hydrogen, use modified ZSM-5 for catalysis
Agent, two sections of fixed bed reactors, operation pressure is 0.1～5.0Mpa, and operation temperature is 300-460 DEG C, and raw material liq air speed is
0.1～6.0h-1Under the conditions of methanol oxidation be converted into the product based on aromatic hydrocarbons, operating condition easily reaches.
2), moving bed methanol aromatic hydrocarbons provided herein and the method for coproduct hydrogen, second segment reactor Main Function
The non-aromatics produced for first paragraph reactor and lower carbon number hydrocarbons aromatisation again, oil phase productivity is more than 40%, wherein arene content
More than 80%, there is total arenes selectivity high, technological operation advantage flexibly.
3), moving bed methanol aromatic hydrocarbons provided herein and the method for coproduct hydrogen, can by by-product again
Utilize yield and the selectivity improving target product aromatic hydrocarbons, and by-product hydrogen, and device achieves continuous prodution.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described.
Fig. 1 is moving bed methanol aromatic hydrocarbons provided herein and the combinative structure schematic diagram of coproduct hydrogen；
1-aromatization of methanol unit, 2-three phase separation unit, 3-gas separation unit, 4-aromatization of low carbon hydrocarbon unit, 5-
Aromatics Extractive Project unit, 6-aromatic hydrocarbons rectification cell.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will
Understanding, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.In embodiment unreceipted specifically
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, be
Can be by the commercially available conventional products bought and obtain.
Embodiment 1
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.3Mpa,
Reaction temperature 380 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content is 4%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatics and mixing aromatic hydrocarbons,
Mixing aromatic hydrocarbons enters rectifier unit and is further separated into BTX and C9 +Aromatic hydrocarbons, aromatization of methanol reacts the gaseous product (hydrogen produced
Gas, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatics product of Aromatics Extractive Project unit gained together enter low
Carbon alkane moving bed aromatisation unit, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, wherein Zn
Content is 4%, reaction temperature 460 DEG C, pressure 0.4Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen, other
Low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 2
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.3Mpa,
Reaction temperature 400 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content is 4%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatics and mixing aromatic hydrocarbons,
Mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, aromatization of methanol reacts the gaseous product (hydrogen produced
Gas, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatics product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, its
Middle Zn content is 4%, reaction temperature 460 DEG C, pressure 0.4Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen,
Other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 3
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.3Mpa,
Reaction temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content is 4%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatics and mixing aromatic hydrocarbons,
Mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, aromatization of methanol reacts the gaseous product (hydrogen produced
Gas, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatics product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, its
Middle Zn content is 4%, reaction temperature 460 DEG C, pressure 0.4Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen,
Other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 4
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.3Mpa,
Reaction temperature 430 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content is 4%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatics and mixing aromatic hydrocarbons,
Mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, aromatization of methanol reacts the gaseous product (hydrogen produced
Gas, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatics product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, its
Middle Zn content is 4%, reaction temperature 460 DEG C, pressure 0.4Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen,
Other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 5
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.3Mpa,
Reaction temperature 380 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 3%, P content is 5%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatics and mixing aromatic hydrocarbons,
Mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, aromatization of methanol reacts the gaseous product (hydrogen produced
Gas, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatic product of Aromatics Extractive Project unit gained together enter low-carbon (LC)
In alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, wherein
Zn content is 4%, reaction temperature 460 DEG C, pressure 0.4Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen, its
Its low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 6
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.3Mpa,
Reaction temperature 380 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 5%, P content is 4%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatics and mixing aromatic hydrocarbons,
Mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, aromatization of methanol reacts the gaseous product (hydrogen produced
Gas, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatic product of Aromatics Extractive Project unit gained together enter low-carbon (LC)
In alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, wherein
Zn content is 4%, reaction temperature 460 DEG C, pressure 0.4Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen, its
Its low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 7
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.4Mpa,
Temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P-Ag be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content 5%, Ag content 1%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatic and mixed
And aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gaseous product of aromatization of methanol unit
(hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatic product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, its
Middle Zn content is 5%, reaction temperature 480 DEG C, pressure 0.6Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen,
Other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 8
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.4Mpa,
Temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P-Ag be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content 5%, Ag content 1%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatic and mixed
And aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gaseous product of aromatization of methanol unit
(hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatic product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, its
Middle Zn content is 5%, reaction temperature 500 DEG C, pressure 0.6Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen,
Other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 9
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.4Mpa,
Temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P-Ag be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content 5%, Ag content 1%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatic and mixed
And aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gaseous product of aromatization of methanol unit
(hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatic product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst is the ZSM-5 catalyst that silica alumina ratio is 60 modified for Zn, its
Middle Zn content is 5%, reaction temperature 520 DEG C, pressure 0.5Mpa, reciprocal of duty cycle 0.6h-1, in product tail gas, hydrogen is former as refinery's hydrogen,
Other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 10
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.4Mpa,
Temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P-Ag be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content 2%, P content 5%, Ag content 1%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-aromatic and mixed
And aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gaseous product of aromatization of methanol unit
(hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and the non-aromatic product of Aromatics Extractive Project unit gained together enter low
In carbon alkane moving bed aromatization reactor, reaction used catalyst be the composite modified silica alumina ratio of Zn, P and Ag be 60
HZSM-5 molecular sieve catalyst, wherein Zn content 2%, P content is 4%, and Ag content is 2%, reaction temperature 480 DEG C, pressure
0.6Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen, and other low-carbon alkanes uses as fuel gas, and liquid phase is produced
Thing enters Aromatics Extractive Project unit.
Embodiment 11
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.5Mpa,
Temperature 420 DEG C, reaction used catalyst is the HZSM-5 molecular sieve catalyst that silica alumina ratio is 60 that Zn, P and Ga are composite modified, its
Middle Zn content is 3%, and P content is 4%, and Ga content is 2%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-
Virtue and mixing aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gas of aromatization of methanol unit
The non-aromatic product of body product (hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and Aromatics Extractive Project unit gained is together
Entering in low-carbon alkanes moving bed aromatization reactor, the ZSM-5 that silica alumina ratio is 60 that reaction used catalyst is modified for Zn urges
Agent, wherein Zn content is 3%, reaction temperature 520 DEG C, pressure 0.5Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is as refining
Factory's hydrogen is former, and other low-carbon alkanes uses as fuel gas, and liquid product enters Aromatics Extractive Project unit.
Embodiment 12
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.5Mpa,
Temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P-Ga be the HZSM-5 molecular sieve catalyst of 60, its
In, Zn content is 3%, and P content is 4%, and Ga content is 2%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-
Virtue and mixing aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gas of aromatization of methanol unit
The non-aromatic product of body product (hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and Aromatics Extractive Project unit gained is together
Enter in low-carbon alkanes moving bed aromatization reactor, reaction used catalyst be the composite modified silica alumina ratio of Zn, P and Ga be 60
HZSM-5 molecular sieve catalyst, wherein Zn content 2%, P content is 3%, and Ga content is 1%, reaction temperature 520 DEG C, pressure
0.5Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen, and other low-carbon alkanes uses as fuel gas, and liquid phase is produced
Thing enters Aromatics Extractive Project unit.
Embodiment 13
Methanol enters aromatization of methanol moving-burden bed reactor, and methanol Feed space velocities is 0.8h-1, reaction pressure is 0.5Mpa,
Temperature 420 DEG C, reaction used catalyst be silica alumina ratio composite modified for Zn-P-Ga be the HZSM-5 molecular sieve catalyst of 60, its
Middle Zn content is 3%, and P content is 4%, and Ga content is 2%.Reaction gained oil-phase product enters Aromatics Extractive Project unit, separates non-
Virtue and mixing aromatic hydrocarbons, mixing aromatic hydrocarbons enters rectifier unit and is further separated into B, T, X and C9 +Aromatic hydrocarbons, the gas of aromatization of methanol unit
The non-aromatic product of body product (hydrogen, methane, ethylene, propane, propylene, iso-butane, 1 butylene) and Aromatics Extractive Project unit gained is together
Enter in low-carbon alkanes moving bed aromatization reactor, reaction used catalyst be the composite modified silica alumina ratio of Zn, P and Ga be 60
HZSM-5 molecular sieve catalyst, wherein Zn content 2%, P content is 5%, and Ga content is 0.5%, reaction temperature 520 DEG C, pressure
Power 0.5Mpa, reciprocal of duty cycle 0.5h-1, in product tail gas, hydrogen is former as refinery's hydrogen, and other low-carbon alkanes uses as fuel gas, liquid phase
Product enters Aromatics Extractive Project unit.
Embodiment 14
A kind of moving bed methanol aromatic hydrocarbons that the present embodiment is provided and the device of coproduct hydrogen, including aromatization of methanol unit
1, three phase separation unit 2, gas separation unit 3, Aromatics Extractive Project unit 5, aromatic hydrocarbons rectification cell 6 and aromatization of low carbon hydrocarbon unit 4；
Wherein, the outlet of described aromatization of methanol unit 1 connects with described three phase separation unit 2 entrance, described three phase separation
The gaseous phase outlet of unit 2 connects with described gas separation unit 3 and described Aromatics Extractive Project unit 5 respectively with oil phase outlet, described
The liquefied gas outlet of gas separation unit 3 connects with the entrance of described aromatization of low carbon hydrocarbon unit 4, described aromatization of low carbon hydrocarbon list
Unit's gaseous phase outlet of 4 connect with the entrance of described gas separation unit 3, the oil phase of described aromatization of low carbon hydrocarbon unit 4 export and
The entrance of described Aromatics Extractive Project unit 5 is connected, non-aromatics outlet and the described aromatization of low carbon hydrocarbon of described Aromatics Extractive Project unit 5
The entrance of unit 4 is connected, and the aromatic hydrocarbons outlet of described Aromatics Extractive Project unit 5 connects with described aromatic hydrocarbons rectification cell 6.
Further, aromatization of methanol unit can be aromatization of methanol moving-burden bed reactor, aromatization of low carbon hydrocarbon unit
It can be low-carbon alkanes moving bed aromatization reactor.
Experimental example 1 embodiment 1-13 end product test analysis
Moving bed methanol aromatic hydrocarbons that embodiment 1-13 is provided and the method for coproduct hydrogen, end product is distributed such as table 1 institute
Show.
Table 1 end product analysis result
Test result indicate that, moving bed methanol aromatic hydrocarbons provided herein and the method for coproduct hydrogen, oil phase productivity is big
In 40%, wherein arene content is more than 80%, has total arenes selectivity high, technological operation advantage flexibly.Can be methanol
By-product in aromatisation recycles, and improves yield and the selectivity of aromatic hydrocarbons, and technique is flexible, can be according to market need
Changes persuing target product.
In sum, moving bed methanol aromatic hydrocarbons provided herein and the method for coproduct hydrogen, use modified ZSM-5
For catalyst, two sections of fixed bed reactors, operation pressure is 0.1～5.0Mpa, and operation temperature is 300-460 DEG C, raw material liq
Air speed is 0.1～6.0h-1Under the conditions of methanol oxidation be converted into the product based on aromatic hydrocarbons, operating condition easily reaches.Wherein,
Second stage reactor primarily serves the purpose of non-aromatics and the lower carbon number hydrocarbons aromatisation again that first paragraph reactor produces, and oil phase productivity is more than
40%, wherein arene content is more than 80%, has total arenes selectivity high, technological operation advantage flexibly.Meanwhile, can pass through
By-product again with improving the yield of target product aromatic hydrocarbons and selectivity, and by-product hydrogen, and device achieves continuously
Metaplasia is produced.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
May be made that in the case of spirit and scope many other change and amendment.It is, therefore, intended that in the following claims
Including all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a moving bed methanol aromatic hydrocarbons and the method for coproduct hydrogen, it is characterised in that comprise the following steps:
1) methanol carries out aromatization, and product enters step 2)；
2) from step 1) product enter three phase separation unit carry out isolated gas, oil-phase product and water；Oil phase
Product enters step 3), gas enters step 4)；
3) to from step 2) oil-phase product carry out Aromatics Extractive Project, oil-phase product is separated into non-aromatics and low-carbon (LC) mixing virtue
Hydrocarbon, non-aromatics enters step 5 after raffinating oil), mixing aromatic hydrocarbons enters step 6)；
4) to from step 2) and step 4) gaseous product separate, obtain dry gas and liquefied gas, dry gas is inhaled by transformation
As fuel gas after attached recovery hydrogen, liquefied gas enters step 5)；
5) to from step 4) liquefied gas and step 3) non-aromatics product carry out aromatic hydrocarbons structureization reaction, reaction generate gas
Product enters step 4), oil-phase product enters Aromatics Extractive Project and enters step 3)；
6) to from step 3) low-carbon (LC) mixing aromatic hydrocarbons enter aromatic hydrocarbons rectification cell, isolate BTX and C9 +Aromatic hydrocarbons.
Moving bed methanol aromatic hydrocarbons the most according to claim 1 and the method for coproduct hydrogen, it is characterised in that in step 1)
In, it is moving-burden bed reactor that described methanol carries out the reacton of aromatization.
Moving bed methanol aromatic hydrocarbons the most according to claim 1 and the method for coproduct hydrogen, it is characterised in that in step 1)
In,
The condition of described aromatization is air speed 0.1～3.0h-1, temperature 380～450 DEG C and pressure 0.1-2.0MPa.
Moving bed methanol aromatic hydrocarbons the most according to claim 1 and the method for coproduct hydrogen, it is characterised in that in step 1)
In, the catalyst used by described aromatization be catalyst be the ZSM-5 catalyst modified with Zn, P, Ag and Ga, wherein,
The silica alumina ratio of ZSM-5 catalyst is 36～100.
Moving bed methanol aromatic hydrocarbons the most according to claim 4 and the method for coproduct hydrogen, it is characterised in that described Zn, P,
In the ZSM-5 catalyst that Ag and Ga is modified, modifying element Zn accounts for the 1%～6% of total catalyst weight, preferred 2%～4%；
Modifying element P accounts for the 2%～10% of total catalyst weight, preferred 3%～6%；
Modifying element Ag accounts for the 1%～4% of total catalyst weight, preferred 2%～3%；
Modifying element Ga accounts for the 0.5%～5% of total catalyst weight, preferred 2%～4%.
Moving bed methanol aromatic hydrocarbons the most according to claim 6 and the method for coproduct hydrogen, it is characterised in that described Zn, P,
In the ZSM-5 catalyst that Ag and Ga is modified, modified metal element combines in the way of Zn-P, Zn-P-Ag or Ga-P.
Moving bed methanol aromatic hydrocarbons the most according to claim 1 and the method for coproduct hydrogen, it is characterised in that in step 5)
In, the reactor of described aromatization is fixed bed or moving-burden bed reactor.
Moving bed methanol aromatic hydrocarbons the most according to claim 1 and the method for coproduct hydrogen, it is characterised in that in step 5)
In, the condition of described aromatic hydrocarbons structureization reaction is reaction temperature 450-550 DEG C, and Feed space velocities is 0.5～1.0h-1With pressure 0.2-
0.8Mpa。
Moving bed methanol aromatic hydrocarbons the most according to claim 1 and the method for coproduct hydrogen, it is characterised in that in step 5)
In, the catalyst used by the reaction of described aromatic hydrocarbons structureization is HZSM-5 molecular sieve catalyst modified for Zn；
Preferably, in modified for described Zn HZSM-5 molecular sieve catalyst modifying element Zn account for total catalyst weight 1%～
8%, preferred 2%～5%.
10. moving bed methanol aromatic hydrocarbons and the device of coproduct hydrogen, it is characterised in that include aromatization of methanol unit, three phase separation
Unit, gas separation unit, Aromatics Extractive Project unit, aromatic hydrocarbons rectification cell and aromatization of low carbon hydrocarbon unit；
Wherein, the outlet of described aromatization of methanol unit connects with described three phase separation unit entrance, described three phase separation unit
Gaseous phase outlet connects with described gas separation unit and described Aromatics Extractive Project unit respectively with oil phase outlet, and described gas separates single
The liquefied gas outlet of unit connects with the entrance of described aromatization of low carbon hydrocarbon unit, the gaseous phase outlet of described aromatization of low carbon hydrocarbon unit
Connect with the entrance of described gas separation unit, oil phase outlet and the described Aromatics Extractive Project unit of described aromatization of low carbon hydrocarbon unit
Entrance be connected, the outlet of the non-aromatics of described Aromatics Extractive Project unit is connected with the entrance of described aromatization of low carbon hydrocarbon unit, institute
The aromatic hydrocarbons outlet stating Aromatics Extractive Project unit connects with described aromatic hydrocarbons rectification cell.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521244A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and device for reducing by-products in circulating hydrogen in hydro-static bed reaction system |
| CN112521243A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and system for long-period running toluene-methanol methylation reaction |
| CN113121296A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Method for producing light aromatic hydrocarbon |
| CN113371694A (en) * | 2021-07-16 | 2021-09-10 | 中国石油化工股份有限公司 | Method and device for preparing carbon nano tube and hydrogen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045505A (en) * | 2013-03-15 | 2014-09-17 | 中石化洛阳工程有限公司 | Method for preparing low carbon aromatic hydrocarbons from methanol, and apparatus thereof |
| CN104892346A (en) * | 2014-03-07 | 2015-09-09 | 中石化洛阳工程有限公司 | Method and apparatus for preparing p-xylene from methanol |
-
2016
- 2016-08-10 CN CN201610653577.1A patent/CN106278793A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045505A (en) * | 2013-03-15 | 2014-09-17 | 中石化洛阳工程有限公司 | Method for preparing low carbon aromatic hydrocarbons from methanol, and apparatus thereof |
| CN104892346A (en) * | 2014-03-07 | 2015-09-09 | 中石化洛阳工程有限公司 | Method and apparatus for preparing p-xylene from methanol |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521244A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and device for reducing by-products in circulating hydrogen in hydro-static bed reaction system |
| CN112521243A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and system for long-period running toluene-methanol methylation reaction |
| CN112521243B (en) * | 2019-09-19 | 2023-07-04 | 中国石油化工股份有限公司 | Method and system for long-period running toluene methanol methylation reaction |
| CN112521244B (en) * | 2019-09-19 | 2023-08-04 | 中国石油化工股份有限公司 | Method and device for reducing byproducts in circulating hydrogen in hydrogen-contacting fixed bed reaction system |
| CN113121296A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Method for producing light aromatic hydrocarbon |
| CN113121296B (en) * | 2020-01-15 | 2022-12-02 | 中国石油天然气股份有限公司 | Method for producing light aromatic hydrocarbon |
| CN113371694A (en) * | 2021-07-16 | 2021-09-10 | 中国石油化工股份有限公司 | Method and device for preparing carbon nano tube and hydrogen |
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