CN106431808A - Method for preparing aromatic hydrocarbons from methanol and liquefied gas - Google Patents
Method for preparing aromatic hydrocarbons from methanol and liquefied gas Download PDFInfo
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Abstract
The invention relates to a method for preparing aromatic hydrocarbons from methanol and liquefied gas. The method comprises the following steps: 1, filling a fixed bed reactor with a metal cadmium modified ZSM-5 molecular sieve catalyst, wherein the metal cadmium accounts for 0.01-5% of the total weight of the ZSM-5 molecular sieve catalyst; 2, processing the ZSM-5 molecular sieve catalyst in the presence of an inert gas; and 3, adjusting the temperature to a reaction temperature and the pressure to a reaction pressure, inputting methanol and liquefied gas to a preheating mixer at the top end of the reactor, carrying out gasification and mixing, adding the obtained mixture to a reactor, and carrying out a reaction to generate the above product. The methanol conversion rate is 99.9%, and the selectivity of aromatic hydrocarbons in the liquid phase product is 80-92%. The method for preparing aromatic hydrocarbons from methanol and liquefied gas has the advantages of effective improvement of the economic added values of methanol and liquefied gas, low raw material cost and simple preparation process.
Description
Technical field
The invention belongs to aromatics production field is and in particular to one kind prepares virtue with methanol and liquefied gas for raw material
The method of hydrocarbon.
Background technology
Aromatic hydrocarbons is important industrial chemicals, and including benzene,toluene,xylene etc., aromatic hydrocarbons still mainly passes through oil
Catalytic reforming and catalytic pyrolysiss produce, heavy dependence petroleum resources.Ended for the end of the year 2013, domestic have first
189 sets of alcohol production device, 5213.5 ten thousand tons of aggregated capacity.And the actual production of 2014 only 37,000,000
About ton, production capacity is seriously superfluous.In the oil refining such as catalytic cracking, methanol-to-olefins and chemical process
In, often by-product liquefied gas, liquefied gas is worth not high directly as fuel utilization.With methanol or liquid
Activating QI is raw material production aromatic hydrocarbons product, can widen the raw material sources of aromatics production.
US3931349 discloses the method with methanol for raw material production gasoline earliest,
201010146915.5th, CN1923770A, the patents such as 201010261587.3 all disclose and with methanol are
Raw material production includes the hydrocarbon manufacturing process of aromatic component.201010261708.4、CN1880288A、
201110219890.1 disclosing the preparation producing the hydrocarbon catalytic agent including aromatic component for methanol conversion
Method.Patent CN103694078A discloses the method preparing aromatic hydrocarbons for raw material with methanol and butylene,
At 400～500 degrees Celsius, 0.1～5 MPa, the mol ratio 1～9 of methanol and butylene, methanol weight (hourly) space velocity (WHSV)
Under the conditions of 1～10 is hourly, aromatics yield is up to 78.7%.Patent CN102199069A discloses
A kind of methanol and the co-fed method producing aromatic hydrocarbons of direct steaming gasoline, at 350～500 degrees Celsius, 0.1～1.2
MPa, methanol and direct steaming gasoline mass ratio are 0.1～10, and methanol and direct steaming gasoline weight (hourly) space velocity (WHSV) are 1～10
Under the conditions of per hour, in product, the yield of aromatic hydrocarbons is more than 60%.Patent CN1586721A discloses
A kind of carbon four liquefied petroleum gas aromatization catalyst and preparation method thereof, in prepared catalyst
On, 400 degrees Celsius, 3 MPas, liquefied gas weight (hourly) space velocity (WHSV) be 0.8 hourly under the conditions of, liquefied gas
Conversion ratio is more than 97%, and the liquid hydrocarbon yield of carbon more than five is 70～74%, and wherein arene content exists
46～53%.
But, aromatic hydrocarbons is produced using liquefied gas through aromatization and easily generates heavy arene, be to lead to aromatisation anti-
Answer the main cause of catalyst inactivation；Aromatization of methanol reacts for strong exothermal reaction, especially in fixed bed
In reactor, heat is difficult to be removed, therefore reaction difficult to reach balance, and reactor can be caused to fly simultaneously
Temperature and make catalyst inactivate, additionally, still there is a problem of that aromatics yield is relatively low at present
Content of the invention
It is an object of the invention to provide a kind of method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas, with
Overcome the relatively low problem of aromatics yield in prior art.
The object of the present invention is achieved like this, a kind of prepares the side of aromatic hydrocarbons with methanol and liquefied gas for raw material
Method, comprises the following steps：
(1) by ZSM-5 molecular sieve Catalyst packing modified for cadmium metal in fixed bed reactors,
Cadmium metal accounts for the 0.01～5% of ZSM-5 molecular sieve total catalyst weight；
(2) under conditions of being passed through noble gases, ZSM-5 molecular sieve catalyst is processed；
And
(3) temperature is adjusted to reaction temperature, pressure is adjusted to reaction pressure, by methanol and liquefied gas
The preheating mixer on input reactor top, enters reactor reaction after gasification and mixing, generates and produces
Thing.
Wherein, with the modified ZSM-5 molecular sieve of cadmium metal as catalyst, methanol and liquefied gas enter altogether
Aromatic hydrocarbons is prepared in material reaction.
Wherein, described ZSM-5 molecular sieve silica alumina ratio is 20～100, preferably 30～70.
Wherein, in described modified ZSM-5 molecular sieve catalyst, cadmium metal accounts for ZSM-5 molecular sieve
The percentage ratio of total catalyst weight is preferably 0.1～3%.
Wherein, described ZSM-5 molecular sieve Catalyst packing constant temperature zone in the middle part of fixed bed reactors.
Wherein, described noble gases are nitrogen, helium or argon.
Wherein, in described step (2), ZSM-5 molecular sieve catalyst treatment temperature is Celsius for 300～700
Degree, process time is 0.5-5 hour；It is preferably treatment temperature and be 400～600 degrees Celsius, process time
For 1～3 hour.
Wherein, described methanol concentration is 90～100%, preferably 95～100%.
Wherein, in described liquefied gas composition, the molar concentration rate of alkane and alkene is 0.5～20, preferably
1～10.
Wherein, described reaction temperature is 350～550 degrees Celsius, and reaction pressure is 0.01～3 MPa, first
Alcohol and liquefied gas raw materials components mole ratio example are 0.01～2, and weight space velocity is 0.1～10 hour-1；It is preferably and react
400～500 degrees Celsius of temperature, 0.1～1.5 MPa of reaction pressure, methanol and liquefied gas raw materials components mole ratio example
It is preferably 0.2～1, weight space velocity is preferably 1～5 hour-1.
Beneficial effects of the present invention：
Methanol and the co-fed method producing aromatic hydrocarbons of liquefied gas that the present invention provides, methanol dehydroxylation is formed greatly
The free radical hybrid reaction that in amount methyl free radicals, with liquefied gas, olefinic protons, alkane cracking are formed,
Light aromatics, the especially yield of benzene, toluene and dimethylbenzene can be improved.Meanwhile, alkane in liquefied gas
Cracking reaction is the endothermic reaction, can the problem that removes of effectively solving aromatization of methanol heat difficulty.
Brief description
Fig. 1 is to prepare the process chart of aromatic hydrocarbons with methanol and liquefied gas for raw material；
Wherein, reference：
1st, dosing pump A
2nd, dosing pump B
3rd, air relief valve
4th, effusion meter
5th, reaction mass premix gasifier
6th, pressure gauge
7th, aromatization reactor
8th, gas-liquid separator
9th, oil water separator
10th, on-line analysis system
Specific embodiment
Hereinafter embodiments of the invention are elaborated：The present embodiment is being front with technical solution of the present invention
Put and implemented, give detailed embodiment and process, but protection scope of the present invention is not limited to
Following embodiments, the experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part.
Content in ZSM-5 molecular sieve catalyst for the modified metal cadmium
In the present invention, the percentage ratio that modified metal cadmium accounts for ZSM-5 molecular sieve total catalyst weight is usually
0.01～5%, preferably 0.1～3%, if content in ZSM-5 molecular sieve catalyst for the modified metal cadmium
Less than 0.01%, then in product, arenes selectivity is relatively low, if modified metal cadmium is urged in ZSM-5 molecular sieve
Content in agent is more than 5%, then can block ZSM-5 molecular sieve partial pore, thus leading to catalyst
Activity reduces.
The silica alumina ratio of ZSM-5 molecular sieve catalyst
In the present invention, ZSM-5 molecular sieve silica alumina ratio is usually 20～100, preferably 30～70, if silicon
Aluminum ratio is less than 20, then hydrothermal stability of molecular sieve is poor, if silica alumina ratio is more than 100, acidic zeolite
Weaker, it is unfavorable for the carrying out of aromatization.
The present invention provides a kind of method preparing aromatic hydrocarbons for raw material with methanol and liquefied gas, it is possible to resolve methanol virtue
The strongly exothermic problem rambunctious of structureization, optimized product forms, and improves light aromatics yield, in reaction temperature
For 350～550 degrees Celsius, pressure is 0.01～3 MPa, reactant weight space velocity WHSV(-CH2-)For
0.1～10 hour-1, under conditions of methanol and liquefied gas raw materials components mole ratio example are 0.01～2, methanol conversion
For 99.9%, the arenes selectivity in liquid product is 80～92%, and process is simple, with low cost,
It is suitable for Mirae Corp.ization to promote.
Content involved in the present invention comprises but the content that is not limited in following examples, with reference to
Accompanying drawing prepares device technique flow process and the tool of aromatic hydrocarbons with methanol and liquefied gas for raw material to provided by the present invention
Body embodiment illustrates.
As shown in Figure 1 a kind of adopts said system to prepare the work of aromatic hydrocarbons with methanol and liquefied gas for raw material
Skill is carried out as follows：Catalyst is loaded in the middle part of aromatization reactor, first, noble gases is led to
Cross air relief valve 3, effusion meter 4 and reaction mass premix gasifier 5 to be passed through in aromatization reactor 7,
300～700 degrees Celsius of pretreatment 0.5～5 hour.Then, methanol and liquefied gas are respectively using dosing pump 1
It is passed through reaction mass premix gasifier 5 with dosing pump 2, after being sufficiently mixed uniformly, be passed through aromatization reactor
7, it is converted into the product based on aromatic hydrocarbons under catalyst action.Wherein, reaction temperature is
350～550 degrees Celsius, pressure is 0.01～3 MPa, reactant weight space velocity WHSV(-CH2-)For
0.1～10 hour-1, methanol and liquefied gas raw materials components mole ratio example are 0.01～2；Pressure gauge 6 is used for monitoring instead
Answer system pressure.Product initially enters gas-liquid separator 8 and is separated into gas phase and liquid product, gas phase
Product enters on-line analysis system 10 and is analyzed；Liquid product enters oil water separator 9 and is separated into oil
Phase and aqueous phase.
Embodiment 1
It is broken into after 20 grams of Hydrogen ZSM-5 molecular sieves (Zeolyst, silica alumina ratio is 20) tabletting
The sample of 20～40 mesh, the nitre being 0.01% by the molecular sieve of molding in 20 grams of concentration under agitation
Impregnate in sour cadmium solution 12 hours, subsequently dry 12 hours in 120 degrees Celsius of air dry oven,
Proceed in 550 degrees Celsius of lower roastings 5 hours in Muffle furnace, prepared cadmium load capacity is that 0.01% modification is urged
Agent, is labeled as Cat-1.2 grams of catalyst Cat-1 are taken to load the flat-temperature zone in the middle part of fixed bed reactors
Interior, in 550 degrees Celsius of pretreatment 2 hours under the atmosphere being passed through inert nitrogen gas.Adjustment reactant
Be pressure to 0.4 MPa, system temperature is down to 350 degrees Celsius of reaction temperature simultaneously, stops being passed through nitrogen
Gas, respectively by pump by concentration be 95% methanol and liquefaction pneumatic transmission that alkane, olefin molar ratio are 5
Enter preheating mixer, the molar ratio of methanol and liquefied gas is 0.4, input after preheated and mixing is fixed
The total weight space velocity WHSV of bed reactor, methanol and liquefied gas charging(-CH2-)For 2 per hour.Product
It is divided into gas phase and liquid phase after condensed.Gas-phase product is online through SP3420A and GC8600 gas chromatogram
Analysis, nitrogen is as internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, split-phase
Weigh its weight afterwards respectively.Oil phase is by the gas chromatogram inspection with KB-Wax chromatographic column and FID
Survey, with n-butyl alcohol as internal standard substance, on the gas chromatogram of OV-01 chromatographic column and FID, aqueous phase is entered
Row detection, obtains methanol content therein, thus trying to achieve the conversion ratio of methanol.Produced by gas phase and liquid phase
Each component analyses in thing, obtain the CH balance of course of reaction, its error control is within 5%.First
Alcohol conversion is 99.9%, and in liquid product, the selectivity of aromatic hydrocarbons is 89%.
Embodiment 2
It is broken into after 20 grams of Hydrogen ZSM-5 molecular sieves (Zeolyst, silica alumina ratio is 50) tabletting
The sample of 20～40 mesh, the nitre being 0.01% by the molecular sieve of molding in 20 grams of concentration under agitation
Impregnate in sour cadmium solution 12 hours, subsequently dry 12 hours in 120 degrees Celsius of air dry oven,
Proceed in 550 degrees Celsius of lower roastings 5 hours in Muffle furnace, prepared cadmium load capacity is that 0.01% modification is urged
Agent, is labeled as Cat-2.2 grams of catalyst Cat-2 are taken to load the flat-temperature zone in the middle part of fixed bed reactors
Interior, in 550 degrees Celsius of pretreatment 2 hours under the atmosphere being passed through inert nitrogen gas.Adjustment reactant
Be pressure to 0.4 MPa, system temperature is down to 350 degrees Celsius of reaction temperature simultaneously, stops being passed through nitrogen
Gas, respectively by pump by concentration be 95% methanol and liquefaction pneumatic transmission that alkane, olefin molar ratio are 5
Enter preheating mixer, the molar ratio of methanol and liquefied gas is 0.4, input after preheated and mixing is fixed
The total weight space velocity WHSV of bed reactor, methanol and liquefied gas charging(-CH2-)For 2 per hour.Product
It is divided into gas phase and liquid phase after condensed.Gas-phase product is online through SP3420A and GC8600 gas chromatogram
Analysis, nitrogen is as internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, split-phase
Weigh its weight afterwards respectively.Oil phase is by the gas chromatogram inspection with KB-Wax chromatographic column and FID
Survey, with n-butyl alcohol as internal standard substance, on the gas chromatogram of OV-01 chromatographic column and FID, aqueous phase is entered
Row detection, obtains methanol content therein, thus trying to achieve the conversion ratio of methanol.Produced by gas phase and liquid phase
Each component analyses in thing, obtain the CH balance of course of reaction, its error control is within 5%.First
Alcohol conversion is 99.9%, and in liquid product, the selectivity of aromatic hydrocarbons is 86%.
Embodiment 3
It is broken into after 20 grams of Hydrogen ZSM-5 molecular sieves (Zeolyst, silica alumina ratio is 100) tabletting
The sample of 20～40 mesh, the nitre being 0.01% by the molecular sieve of molding in 20 grams of concentration under agitation
Impregnate in sour cadmium solution 12 hours, subsequently dry 12 hours in 120 degrees Celsius of air dry oven,
Proceed in 550 degrees Celsius of lower roastings 5 hours in Muffle furnace, prepared cadmium load capacity is that 0.01% modification is urged
Agent, is labeled as Cat-3.2 grams of catalyst Cat-3 are taken to load the flat-temperature zone in the middle part of fixed bed reactors
Interior, in 550 degrees Celsius of pretreatment 2 hours under the atmosphere being passed through inert nitrogen gas.Adjustment reactant
Be pressure to 0.4 MPa, system temperature is down to 350 degrees Celsius of reaction temperature simultaneously, stops being passed through nitrogen
Gas, respectively by pump by concentration be 95% methanol and liquefaction pneumatic transmission that alkane, olefin molar ratio are 5
Enter preheating mixer, the molar ratio of methanol and liquefied gas is 0.4, input after preheated and mixing is fixed
The total weight space velocity WHSV of bed reactor, methanol and liquefied gas charging(-CH2-)For 2 per hour.Product
It is divided into gas phase and liquid phase after condensed.Gas-phase product is online through SP3420A and GC8600 gas chromatogram
Analysis, nitrogen is as internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, split-phase
Weigh its weight afterwards respectively.Oil phase is by the gas chromatogram inspection with KB-Wax chromatographic column and FID
Survey, with n-butyl alcohol as internal standard substance, on the gas chromatogram of OV-01 chromatographic column and FID, aqueous phase is entered
Row detection, obtains methanol content therein, thus trying to achieve the conversion ratio of methanol.Produced by gas phase and liquid phase
Each component analyses in thing, obtain the CH balance of course of reaction, its error control is within 5%.First
Alcohol conversion is 99.9%, and in liquid product, the selectivity of aromatic hydrocarbons is 80%.
Embodiment 4
It is broken into after 20 grams of Hydrogen ZSM-5 molecular sieves (Zeolyst, silica alumina ratio is 50) tabletting
The sample of 20～40 mesh, the nitric acid being 2.6% by the molecular sieve of molding in 20 grams of concentration under agitation
Impregnate in cadmium solution 12 hours, subsequently dry 12 hours in 120 degrees Celsius of air dry oven, turn
Enter in 550 degrees Celsius of lower roastings 5 hours in Muffle furnace, prepared cadmium load capacity is 2.5% Modified catalytic
Agent, is labeled as Cat-4.2 grams of catalyst Cat-4 are taken to load the flat-temperature zone in the middle part of fixed bed reactors
Interior, in 550 degrees Celsius of pretreatment 2 hours under the atmosphere being passed through inert nitrogen gas.Adjustment reactant
Be pressure to 0.4 MPa, system temperature is down to 350 degrees Celsius of reaction temperature simultaneously, stops being passed through nitrogen
Gas, respectively by pump by concentration be 95% methanol and liquefaction pneumatic transmission that alkane, olefin molar ratio are 5
Enter preheating mixer, the molar ratio of methanol and liquefied gas is 0.4, input after preheated and mixing is fixed
The total weight space velocity WHSV of bed reactor, methanol and liquefied gas charging(-CH2-)For 2 per hour.Product
It is divided into gas phase and liquid phase after condensed.Gas-phase product is online through SP3420A and GC8600 gas chromatogram
Analysis, nitrogen is as internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, split-phase
Weigh its weight afterwards respectively.Oil phase is by the gas chromatogram inspection with KB-Wax chromatographic column and FID
Survey, with n-butyl alcohol as internal standard substance, on the gas chromatogram of OV-01 chromatographic column and FID, aqueous phase is entered
Row detection, obtains methanol content therein, thus trying to achieve the conversion ratio of methanol.Produced by gas phase and liquid phase
Each component analyses in thing, obtain the CH balance of course of reaction, its error control is within 5%.First
Alcohol conversion is 99.9%, and in liquid product, the selectivity of aromatic hydrocarbons is 88%.
Embodiment 5
It is broken into after 20 grams of Hydrogen ZSM-5 molecular sieves (Zeolyst, silica alumina ratio is 50) tabletting
The sample of 20～40 mesh, the nitric acid being 5.3% by the molecular sieve of molding in 20 grams of concentration under agitation
Impregnate in cadmium solution 12 hours, subsequently dry 12 hours in 120 degrees Celsius of air dry oven, turn
Enter in 550 degrees Celsius of lower roastings 5 hours in Muffle furnace, prepared cadmium load capacity is 5% Modified catalytic
Agent, is labeled as Cat-5.2 grams of catalyst Cat-5 are taken to load the flat-temperature zone in the middle part of fixed bed reactors
Interior, in 550 degrees Celsius of pretreatment 2 hours under the atmosphere being passed through inert nitrogen gas.Adjustment reactant
Be pressure to 0.4 MPa, system temperature is down to 350 degrees Celsius of reaction temperature simultaneously, stops being passed through nitrogen
Gas, respectively by pump by concentration be 95% methanol and liquefaction pneumatic transmission that alkane, olefin molar ratio are 5
Enter preheating mixer, the molar ratio of methanol and liquefied gas is 0.4, input after preheated and mixing is fixed
The total weight space velocity WHSV of bed reactor, methanol and liquefied gas charging(-CH2-)For 2 per hour.Product
It is divided into gas phase and liquid phase after condensed.Gas-phase product is online through SP3420A and GC8600 gas chromatogram
Analysis, nitrogen is as internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, split-phase
Weigh its weight afterwards respectively.Oil phase is by the gas chromatogram inspection with KB-Wax chromatographic column and FID
Survey, with n-butyl alcohol as internal standard substance, on the gas chromatogram of OV-01 chromatographic column and FID, aqueous phase is entered
Row detection, obtains methanol content therein, thus trying to achieve the conversion ratio of methanol.Produced by gas phase and liquid phase
Each component analyses in thing, obtain the CH balance of course of reaction, its error control is within 5%.First
Alcohol conversion is 99.9%, and in liquid product, the selectivity of aromatic hydrocarbons is 92%.
Embodiment 6
Take 2 grams of catalyst Cat-5 to load in the flat-temperature zone in the middle part of fixed bed reactors, be passed through indifferent gas
In 550 degrees Celsius of pretreatment 2 hours under the atmosphere of body nitrogen.Adjustment reaction system pressure is to 0.4 million
System temperature is down to 450 degrees Celsius of reaction temperature by handkerchief simultaneously, stops being passed through nitrogen, passes through pump respectively
By concentration be 95% methanol and liquefied gas that alkane, olefin molar ratio are 5 send into preheating mixer,
The molar ratio of methanol and liquefied gas be 0.4, preheated and mixing after input fixed bed reactors, methanol
The weight space velocity WHSV total with liquefied gas charging(-CH2-)For 2 per hour.It is divided into gas after product is condensed
Phase and liquid phase.Gas-phase product is through SP3420A and GC8600 gas chromatogram on-line analyses, nitrogen conduct
Internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, weighs it respectively heavy after split-phase
Amount.Oil phase, by the gas chromatographic detection with KB-Wax chromatographic column and FID, is interior with n-butyl alcohol
Mark thing, is detected to aqueous phase on the gas chromatogram of OV-01 chromatographic column and FID, obtains wherein
Methanol content, thus trying to achieve the conversion ratio of methanol.Divided by each component in gas phase and liquid product
Analysis, obtains the CH balance of course of reaction, its error control is within 5%.Methanol conversion is
99.9%, in liquid product, the selectivity of aromatic hydrocarbons is 87%.
Embodiment 7
Take 2 grams of catalyst Cat-5 to load in the flat-temperature zone in the middle part of fixed bed reactors, be passed through indifferent gas
In 550 degrees Celsius of pretreatment 2 hours under the atmosphere of body nitrogen.Adjustment reaction system pressure is to 0.4 million
System temperature is down to 550 degrees Celsius of reaction temperature by handkerchief simultaneously, stops being passed through nitrogen, passes through pump respectively
By concentration be 95% methanol and liquefied gas that alkane, olefin molar ratio are 5 send into preheating mixer,
The molar ratio of methanol and liquefied gas be 0.4, preheated and mixing after input fixed bed reactors, methanol
The weight space velocity WHSV total with liquefied gas charging(-CH2-)For 2 per hour.It is divided into gas after product is condensed
Phase and liquid phase.Gas-phase product is through SP3420A and GC8600 gas chromatogram on-line analyses, nitrogen conduct
Internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, weighs it respectively heavy after split-phase
Amount.Oil phase, by the gas chromatographic detection with KB-Wax chromatographic column and FID, is interior with n-butyl alcohol
Mark thing, is detected to aqueous phase on the gas chromatogram of OV-01 chromatographic column and FID, obtains wherein
Methanol content, thus trying to achieve the conversion ratio of methanol.Divided by each component in gas phase and liquid product
Analysis, obtains the CH balance of course of reaction, its error control is within 5%.Methanol conversion is
99.9%, in liquid product, the selectivity of aromatic hydrocarbons is 82%.
Embodiment 8
Take 2 grams of catalyst Cat-5 to load in the flat-temperature zone in the middle part of fixed bed reactors, be passed through indifferent gas
In 550 degrees Celsius of pretreatment 2 hours under the atmosphere of body nitrogen.Adjustment reaction system pressure is to 0.4 million
System temperature is down to 350 degrees Celsius of reaction temperature by handkerchief simultaneously, stops being passed through nitrogen, passes through pump respectively
By concentration be 95% methanol and liquefied gas that alkane, olefin molar ratio are 5 send into preheating mixer,
The molar ratio of methanol and liquefied gas be 0.4, preheated and mixing after input fixed bed reactors, methanol
The weight space velocity WHSV total with liquefied gas charging(-CH2-)For 0.1 per hour.It is divided into gas after product is condensed
Phase and liquid phase.Gas-phase product is through SP3420A and GC8600 gas chromatogram on-line analyses, nitrogen conduct
Internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, weighs it respectively heavy after split-phase
Amount.Oil phase, by the gas chromatographic detection with KB-Wax chromatographic column and FID, is interior with n-butyl alcohol
Mark thing, is detected to aqueous phase on the gas chromatogram of OV-01 chromatographic column and FID, obtains wherein
Methanol content, thus trying to achieve the conversion ratio of methanol.Divided by each component in gas phase and liquid product
Analysis, obtains the CH balance of course of reaction, its error control is within 5%.Methanol conversion is
99.9%, in liquid product, the selectivity of aromatic hydrocarbons is 91%.
Embodiment 9
Take 2 grams of catalyst Cat-5 to load in the flat-temperature zone in the middle part of fixed bed reactors, be passed through indifferent gas
In 550 degrees Celsius of pretreatment 2 hours under the atmosphere of body nitrogen.Adjustment reaction system pressure is to 0.4 million
System temperature is down to 350 degrees Celsius of reaction temperature by handkerchief simultaneously, stops being passed through nitrogen, passes through pump respectively
By concentration be 95% methanol and liquefied gas that alkane, olefin molar ratio are 5 send into preheating mixer,
The molar ratio of methanol and liquefied gas be 0.4, preheated and mixing after input fixed bed reactors, methanol
The weight space velocity WHSV total with liquefied gas charging(-CH2-)For 10 per hour.It is divided into gas after product is condensed
Phase and liquid phase.Gas-phase product is through SP3420A and GC8600 gas chromatogram on-line analyses, nitrogen conduct
Internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, weighs it respectively heavy after split-phase
Amount.Oil phase, by the gas chromatographic detection with KB-Wax chromatographic column and FID, is interior with n-butyl alcohol
Mark thing, is detected to aqueous phase on the gas chromatogram of OV-01 chromatographic column and FID, obtains wherein
Methanol content, thus trying to achieve the conversion ratio of methanol.Divided by each component in gas phase and liquid product
Analysis, obtains the CH balance of course of reaction, its error control is within 5%.Methanol conversion is
99.9%, in liquid product, the selectivity of aromatic hydrocarbons is 83%.
Embodiment 10
Take 2 grams of catalyst Cat-5 to load in the flat-temperature zone in the middle part of fixed bed reactors, be passed through indifferent gas
In 550 degrees Celsius of pretreatment 2 hours under the atmosphere of body nitrogen.Adjustment reaction system pressure is to 0.4 million
System temperature is down to 350 degrees Celsius of reaction temperature by handkerchief simultaneously, stops being passed through nitrogen, passes through pump respectively
By concentration be 95% methanol and liquefied gas that alkane, olefin molar ratio are 5 send into preheating mixer,
The molar ratio of methanol and liquefied gas be 0.01, preheated and mixing after input fixed bed reactors, methanol
The weight space velocity WHSV total with liquefied gas charging(-CH2-)For 2 per hour.It is divided into gas after product is condensed
Phase and liquid phase.Gas-phase product is through SP3420A and GC8600 gas chromatogram on-line analyses, nitrogen conduct
Internal standard substance；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, weighs it respectively heavy after split-phase
Amount.Oil phase, by the gas chromatographic detection with KB-Wax chromatographic column and FID, is interior with n-butyl alcohol
Mark thing, is detected to aqueous phase on the gas chromatogram of OV-01 chromatographic column and FID, obtains wherein
Methanol content, thus trying to achieve the conversion ratio of methanol.Divided by each component in gas phase and liquid product
Analysis, obtains the CH balance of course of reaction, its error control is within 5%.Methanol conversion is
99.9%, in liquid product, the selectivity of aromatic hydrocarbons is 90%.
Embodiment 11
Take 2 grams of catalyst Cat-5 to load in the flat-temperature zone in the middle part of fixed bed reactors, be passed through indifferent gas
In 550 degrees Celsius of pretreatment 2 hours under the atmosphere of body nitrogen.Adjustment reaction system pressure is to 0.4 million
System temperature is down to 350 degrees Celsius of reaction temperature by handkerchief simultaneously, stops being passed through nitrogen, passes through pump respectively
By concentration be 95% methanol and liquefied gas that alkane, olefin molar ratio are 5 send into preheating mixer,
The molar ratio of methanol and liquefied gas be 2, preheated and mixing after input fixed bed reactors, methanol and
The total weight space velocity WHSV of liquefied gas charging(-CH2-)For 2 per hour.It is divided into gas phase after product is condensed
And liquid phase., through SP3420A and GC8600 gas chromatogram on-line analyses, nitrogen is as interior for gas-phase product
Mark thing；After cold-trap collection, point liquid is aqueous phase and oil phase to liquid product, weighs it respectively heavy after split-phase
Amount.Oil phase, by the gas chromatographic detection with KB-Wax chromatographic column and FID, is interior with n-butyl alcohol
Mark thing, is detected to aqueous phase on the gas chromatogram of OV-01 chromatographic column and FID, obtains wherein
Methanol content, thus trying to achieve the conversion ratio of methanol.Divided by each component in gas phase and liquid product
Analysis, obtains the CH balance of course of reaction, its error control is within 5%.Methanol conversion is
99.9%, in liquid product, the selectivity of aromatic hydrocarbons is 81%.
Beneficial effects of the present invention：
The present invention passes through the ZSM-5 molecular sieve catalyst modified using cadmium metal etc., and modified metal cadmium exists
Mass content in catalyst is 0.01～5%, it is achieved thereby that with methanol and liquefied gas co-fed preparation virtue
The method of hydrocarbon, aromatics yield is up to 80%～92%；In addition, the methyl that methanol dehydroxylation is formed is freely
The radical reaction that in base, with liquefied gas, olefinic protons, alkane cracking produce can improve light aromatics
Yield, alkane cracking can effectively remove aromatization of methanol reaction liberated heat.Product can effectively be optimized
Composition, also solves the problem that the strongly exothermic problem of aromatization of methanol.
Certainly, the present invention also can have other various embodiments, spiritual and its substantive without departing substantially from the present invention
In the case of, those of ordinary skill in the art can make various corresponding changes according to the present invention and deform,
But these corresponding changes and deformation all should belong to the protection domain of the claims in the present invention.
Claims (9)
1. a kind of the method for aromatic hydrocarbons is prepared it is characterised in that the method for raw material with methanol and liquefied gas
Comprise the following steps：
(1) by ZSM-5 molecular sieve Catalyst packing modified for cadmium metal in fixed bed reactors,
Cadmium metal accounts for the 0.01～5% of ZSM-5 molecular sieve total catalyst weight；
(2) under conditions of being passed through noble gases, ZSM-5 molecular sieve catalyst is processed；With
And
(3) temperature is adjusted to reaction temperature, pressure is adjusted to reaction pressure, by methanol and liquefied gas
The preheating mixer on input reactor top, enters reactor reaction after gasification and mixing, generates and produces
Thing.
2. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, with the modified ZSM-5 molecular sieve of cadmium metal as catalyst, methanol and liquefied gas enter altogether
Aromatic hydrocarbons is prepared in material reaction.
3. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, described ZSM-5 molecular sieve silica alumina ratio is 20～100.
4. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, described ZSM-5 molecular sieve Catalyst packing constant temperature zone in the middle part of fixed bed reactors.
5. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, described noble gases are nitrogen, helium or argon.
6. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, in described step (2), ZSM-5 molecular sieve catalyst treatment temperature is Celsius for 300～700
Degree, process time is 0.5-5 hour.
7. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, described methanol concentration is 90～100%.
8. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, in described liquefied gas composition, the molar concentration rate of alkane and alkene is 0.5～20.
9. the method that aromatic hydrocarbons is prepared for raw material with methanol and liquefied gas according to claim 1, its
It is characterised by, described reaction temperature is 350～550 degrees Celsius, reaction pressure is 0.01～3 MPa, first
Alcohol and liquefied gas raw materials components mole ratio example are 0.01～2, and weight space velocity is 0.1～10 hour-1.
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