CN106146235B - The method that hydrocarbon products is prepared by methanol by one-step method - Google Patents
The method that hydrocarbon products is prepared by methanol by one-step method Download PDFInfo
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- CN106146235B CN106146235B CN201610324242.5A CN201610324242A CN106146235B CN 106146235 B CN106146235 B CN 106146235B CN 201610324242 A CN201610324242 A CN 201610324242A CN 106146235 B CN106146235 B CN 106146235B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention provides the method for preparing hydrocarbon products by methanol by one-step method, including the following steps: 1) methanol of heating is fed in reactor to be converted into hydrocarbon products mixture synthesis gas, the reactor is mounted with acid Si-Al zeolite molecular sieve catalyst；2) synthesis gas of step 1) separates liquid phase part and gas phase portion through cooling；3) gas phase portion enters recycle compressor, and compressed at least part is mixed as recycle stock with material benzenemethanol, Returning reactor；Liquid phase part carries out later separation.
Description
Method field
The present invention relates to the methods for preparing hydrocarbon products by methanol by one-step method, belong to the preparation method field of chemical products.
Background method
Data show that it is 188,800,000,000 tons that Global Oil, which verifies remaining reserves,.It is mainly distributed on Middle East, possesses the world
Petroleum verifies the 61.0% of remaining gross reserves, especially concentrates on Gulf states, Organization of Petroleum Exporting Countries (OPEC).Work as this life
The main problem of boundary stone oil supply and demand pattern is the non-equilibrium state between world oil supply and demand on geological location.That is,
The extremely unbalanced feature on landing pit is presented in world oil in terms of yield and consumption.This Global Oil is distributed and consumes, opens
It adopts the regional lack of uniformity between demand not only to pass by exist, but also more prominent in the future, it is still within suitable period
It is the main problem and structural inconsistency of world oil pattern, and by the more obvious of performance.
The few oil of China's richness coal, contradiction between oil supply and demand are very prominent.As China's economy constantly develops rapidly, to petroleum according to
Rely degree can be higher and higher.Consider from energy resource safety strategy angle, the demand for developing alternative energy source seems especially urgent to China.
Gasoline appearance is transparency liquid, is mainly made of each race's hydro carbons of C4~C10, can be divided into 90 by research octane number (RON)
Number, 93 (92) number, No. 97 three trades mark.Octane number with higher and excellent anti-knock properties, the vaporizer for high compression ratio
On formula petrol engine, the power of engine can be improved, reduce fuel consumption；With good vapo(u)rability and flammability, energy
Guarantee that engine smooth running, burning is complete, carbon deposit is few；With preferable stability, it is not easy out in storing and use process
Existing early oxidation is rotten, non-corrosive to engine components and oil vessel.
Methanol is the foundation stone of petrochemical industry, and by catalytic process appropriate, methanol can be converted into a variety of of petrochemical industry
Product, such as the mixture of ethylene, propylene, aromatic hydrocarbons, alkane and the said goods.Methanol conversion preparation process of gasoline (MTG) be by
The method that a kind of methanol conversion of Mobil company invention prepares gasoline.From 1974, the said firm applied for multinomial related methanol
The patent of gasoline processed is converted, and has built the device that plant-scale methanol converts gasoline processed, success in New Zealand the eighties
The business operating of many years is carried out.See, for example, United States Patent (USP) US3931349, the technique of Mobil uses two-stage reaction (also known as
" two-stage method " or " two-step method "): methanol is first converted into dimethyl ether, dimethyl ether and first using shell and tube isothermal reactor by one section
The mixture of alcohol enters two sections of adiabatic reactors and is converted into gasoline and liquefied petroleum under the action of ZSM-5 molecular sieve catalyst
Gas (LPG, Liquefied Petroleum Gas).
United States Patent (USP) US4579999 discloses the side that another two-stage method methanol converts gasoline fraction section hydrocarbon products processed
Method loads molecular sieve catalyst in one section reactor, methanol is first converted into low-carbon alkene and part C5+Hydrocarbon, by C5+It is cold
But after separating, low-carbon alkene enters second stage reactor, under the action of olefin polymerization catalysis, is further converted into gasoline and evaporates
It is segmented product.
United States Patent (USP) 4689205 discloses a kind of method that hydrocarbon is produced in methanol multi-stage conversion.The method of the patent disclosure with
United States Patent (USP) 4579999 is substantially similar, and in first stage reactor, methanol is converted into C2~C4 under certain temperature and pressure condition
Alkene and part C5+Hydrocarbon, by C5+After hydrocarbon separation, remainder enters second segment reactor, using olefin polymerization catalysis, by the
The low-carbon alkene that one section of reaction generates further is polymerized to the hydrocarbon product of gasoline fraction.The difference is that the side of the patent disclosure
In method, first segment is using fluidized-bed reactor.
Currently, researcher is also constantly carrying out the research of the technique, in the hope of improve reaction efficiency, improve yield,
Reduce discharge of poisonous waste.
Summary of the invention
The present invention provides the method for preparing hydrocarbon products by methanol by one-step method, including the following steps:
1) methanol of heating is fed in reactor to be converted into hydrocarbon products mixture synthesis gas, the reactor dress
It is loaded with acid Si-Al zeolite molecular sieve catalyst；
2) synthesis gas of step 1) separates liquid phase part and gas phase portion through cooling；
3) gas phase portion enters recycle compressor, and compressed at least part is mixed as recycle stock and material benzenemethanol
It closes, Returning reactor；Liquid phase part carries out later separation.
In step 1), material benzenemethanol is preheated first, evaporates and overheats, and is then fed to reactor.The reactor can
To be fixed bed reactors, preferred insulation fix bed reactor.
Material benzenemethanol, which can be, to be obtained, raw material by any carbonaceous material such as coal, natural gas, biomass etc. for Material synthesis
The purity of methanol both can be 70% or more, such as 80%, 85%, 90%, 95%, 99% etc..
Catalyst can be acid Si-Al zeolite molecular sieve catalyst, such as commercially available acid Si-Al zeolite molecular sieve catalytic
Agent, such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, preferably ZSM-5 molecular sieve
Catalyst.The example of the catalyst includes LaHZSM-5 molecular sieve catalyst, is made by following synthetic method:
(1) directed agents synthesize:
Silicon source and deionized water, template are configured to solution A, silicon source, inorganic acid and deionized water are configured to B solution, A
Solution is put into synthesis reactor and stirs evenly, and then under 200-400 revs/min of stirring, B solution is added dropwise in solution A, and kettle is close
It closes, is started to warm up after continuing stirring 10-20 minutes, 120 DEG C of constant temperature are risen to 20-25 hours with 2-5 DEG C/minute of rate by room temperature,
165-170 DEG C is risen to 10-15 DEG C/h again, is cooled, is fitted into airtight bottle and directed agents is made；
The wherein molar ratio SiO of each component2∶Al2O3∶Na2O: template: inorganic acid: H2O=40-80: 1: 7-15: 25-40
:3.0-7.5:2000-4000；
(2) Zeolite synthesis:
Silicon source and directed agents, deionized water are configured to C solution, silicon source, inorganic acid and ionized water are configured to solution D, can
The solution of 0.1-1.0Mol/L is made in dissolubility lanthanum salt, is denoted as E solution, and C solution is put into synthesis reactor, starts with 200-400 revs/min
Speed stirring, then E solution is added, the directed agents for accounting for total volume 5-10% is added, then with 3-5 DEG C/min of rate liter
Solution D is finally added dropwise in kettle by temperature to 50-80 DEG C, and kettle is closed, is started to warm up after continuing stirring 10-20 minutes, by room temperature
With 2-5 DEG C/minute of rate rise to 120 DEG C, constant temperature 20-25 hours, then 155-165 DEG C is risen to 10-15 DEG C/h, constant temperature
20-25 hours, material was drawn off, precipitates, filters by then cooling, cooling, and filter cake is washed till solution pH value in 7-8, through 110-
120 DEG C of drying, roast 3-5 hours at 520-540 DEG C, obtain LaZSM-5 molecular sieve；
The molar ratio of each component as described above are as follows:
SiO2∶Al2O3∶Na2O∶R-NH3: inorganic acid: La3+∶H2O=40-80: 1: 7-15: 25-40: 3.0-7.5: 0.1-
2.0:2000-4000；
(3) catalyst is prepared
LaZSM-5 molecular sieve is subjected to ion exchange by the acid solution of 0.5-1Mol/L, until LaZSM-5 molecular sieve
Na+Content < 0.1 (m) %, then drying, 500-540 DEG C after roasting 3-5 hours, obtain LaHZSM-5 molecular sieve.Then it presses
LaHZSM-5 molecular sieve is added binder with weight percent 100-50: 0-50 of binder and is uniformly mixed, while dense with volume
After drying, catalyst is made after roasting 3-5 hours at 500-540 DEG C in the dilute nitric acid solution kneading and compacting for spending < 5%；
In the method, silicon source can be selected from the silicon-containing materials such as sodium metasilicate, tetraethoxysilance, White Carbon black or silica solution, example
Such as by SiO2、Na2The waterglass that O and deionized water are constituted；Silicon source can be selected from aluminum soluble salts such as aluminum sulfate, aluminum nitrates；Template
Agent can be selected from organic amines such as n-butylamine, ethylenediamine, 1,6- hexamethylene diamine, ethamine；Inorganic acid can be selected from sulfuric acid, nitric acid, salt
Acid, etc. mineral acids；Inorganic base can be selected from sodium hydroxide, sodium carbonate etc.；Binder can be selected from aluminium oxide, diatomite, Bao Shui
The molecular sieve molded common binder such as aluminium stone, silica.
Preferably, catalyst of the invention passes through pre-steaming before starting the reaction, includes the following steps:
(1) catalyst is heated to 120 DEG C, constant temperature 1~5 hour, preferably 3 hours by heat cycles gas；
(2) catalyst is heated to 300 DEG C, constant temperature 1~5 hour, preferably 3 hours；
(3) catalyst is heated to 480 DEG C, constant temperature 1~20 hour, preferably 10 hours；
(4) by cooling catalyst to 430 DEG C, superheated steam is imported, air speed is controlled in for example, about 0.5m3·h-1, with removal
Circulation air；
(5) superheated steam is used, makes catalyzer temperature-elevating to 460 DEG C, constant temperature 10~60 hours, preferably 48 hours；
(6) cool down under nitrogen or air circulation.
Wherein, the heating when the catalyst pre-processes and rate of temperature fall are no more than 35 DEG C/h, preferably smaller than 35 DEG C/h.
In step 2), the hydrocarbon mixture of step 1) is cooled to 25~50 DEG C, preferably 40 DEG C.
According to an embodiment of the invention, being mixed from the overheat methanol steam that methanol gasifying system is come with the circulating air of preheating
It is sent in the synthesis aromatic hydrocarbons reactor that two are currently running afterwards.Synthesizing aromatic hydrocarbons reactor is insulation fix bed reactor.Methanol exists
The mixture of aromatic hydrocarbons, LPG, fuel gas and water is converted into this reactor.The reaction is exothermic reaction.Preferably, by the reaction
Reaction heat utilized by following system: a part is for byproduct steam, then passes through steam preheating, Evaporation of methanol, another part
For heat cycles gas.Wherein, synthesis aromatic hydrocarbons reactor inlet feeding temperature is by synthesizing the heat transfer of aromatic hydrocarbons reactor outlet product
To control.
After the recovered reaction heat of hydrocarbon products mixture synthesis gas, after air cooler and cooler are cooling, in the separator
Be divided into three-phase: gas phase (predominantly light component), aqueous mixtures phase and liquid hydrocarbon phase (mainly include C2+Hydrocarbon).Gas phase is through recycling
Synthesis aromatic hydrocarbons reactor inlet is returned to after air compressor compression enters synthesis aromatic hydrocarbons reactor together with the methanol after overheat.
Biochemical treatment mutually is pumped to through synthesizing aromatics process water containing some methanol, fusel aqueous mixtures.Liquid hydrocarbon, that is, thick stable light hydrocarbon
It is fed directly to aromatics seperation part and is further separated into fuel gas, LPG, stable light hydrocarbon and heavy aromatics.
Liquefied gas knockout tower is mainly used for separating LPG from thick stable light hydrocarbon.The tower bottom product of gas removal tower is main
It is the hydro carbons of C3 or more, is further separated in liquefied gas knockout tower.Overhead product is mainly LPG, and tower bottom product is mainly C4
Above hydro carbons.Overhead product is sent into liquefied gas knockout tower return tank after total condensation, C3/C4 hydrocarbon liquid phase a part is back to
Liquefied gas knockout tower, another part is as LPG product.LPG product is sent to tank field through circulating water to 46 DEG C later.Part tower
Bottom product is pumped to absorption tower after cooler is cooling by flow control.Materials at bottom of tower enters product knockout tower and further divides
From.
Product knockout tower is fed mainly from liquefied gas knockout tower tower bottom product.Aromatics seperation is light group by product knockout tower
Divide hydrocarbon (overhead product) and heavy constituent hydrocarbon (tower bottom product).Overhead product total condensation is stable light hydrocarbon, through circulating water
After send to tank field.
For reduce in thick stable light hydrocarbon separating tank gas phase and gas removing tower overhead product low boiling component loss,
It uses partial liquefaction gas knockout tower tower bottom product stable light hydrocarbon as absorbent in absorption tower, this two bursts of gas phases is carried out at absorption
Reason.
According to the present invention, reactor inlet temperature is 305~315 DEG C, preferably 310 DEG C；Outlet temperature is 390 DEG C -420
DEG C, preferably 400~420 DEG C.
Reactor inlet pressure is 1.5~1.8MPa, preferably 1.5~1.6MPa；Outlet pressure is 1.5~1.7MPa, excellent
Select 1.6MPa.
The liquid air speed of methanol is 0.1~80.0m3·h-1, preferably 5~20m3·h-1, such as 10~12m3·h-1。
Recycle stock and material benzenemethanol mass ratio (" recycle ratio ") are 10~20:1, preferably 7~8:1.
It in step 3), is also parsed by absorption tower through the compressed gas phase portion of recycle compressor, separation includes C1 and C2
Light components, the light components first pass around dehydration, then isolate carbon monoxide, carbon dioxide, C2 and C2 or more hydro carbons
Component drains into blow-down pipe and removes torch burning, and the methane of enrichment is sent into natural gas after compressor is compressed to 25MPa from 0.5MPa
Storage tank.
According to the present invention, in the reaction process of synthesis aromatic hydrocarbons, the surface of catalyst can generate carbon distribution, thus using synthesis
Aromatic hydrocarbons reactor regenerative system regenerates the catalyst of inactivation to restore its activity.Preferably, the present invention synthesizes aromatic hydrocarbons
3 synthesis aromatic hydrocarbons reactors are provided in device, the production capacity of each reactor is the 50% of overall design production capacity.
As example, wherein 2 operations, 1 is used for regeneration or spare.
It is described to regenerate or including purification, pressurization, decompression, emptying and the purging before and after carbon distribution burning.Preferably, pass through control
System burning removes carbon distribution from catalyst.
The present invention also provides the acid Si-Al zeolite molecular sieve catalysts Jing Guo decatize, such as by the commercially available of decatize
ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and LaHZSM-5 catalyst.This
Invention further provides purposes of the catalyst in the method for preparing hydrocarbon products by methanol by one-step method.
The beneficial effect comprise that
Method of the invention can by methanol it is highly selective prepare gasoline, and obtained gasoline has higher octane
Value, induction period can reach the requirement of national standard.
Method of the invention recycles the light components of C1 and C2, improves the rate of recovery of by-product.
By pre-steaming, the catalyst efficiency is improved, and can handle the higher raw material of liquid air speed.And
And the service life of the catalyst is also improved, after every regeneration is primary, the service life of processing high liquid air speed raw material is more than 20
It.
Process conditions of the invention mitigate, and run smoothly, easily operated, reduce the cost of commercial scale.
Specific embodiment
Method of the invention is illustrated below in conjunction with specific embodiment, is described in further detail, but should not be incited somebody to action
This is interpreted as the scope of the present invention and is only limitted to example below.Without departing from the idea of the above method of the present invention, according to
The various replacements or change that this field commonsense method knowledge and customary means are made, should be included in the scope of the present invention.
It is conventional method unless otherwise specified in the experimental method；The reagent and material, unless otherwise specified,
Commercially obtain.
Embodiment 1
1. the preparation of catalyst
A. the synthesis of directed agents
The molar ratio group of directed agents becomes SiO2∶Al2O3∶Na2O: n-butylamine: H2SO4∶H2O=40: 1: 10: 28: 7.2:
2800.Silicon source is using composition are as follows: SiO2=25.13%；Na2O=8.12%；H2The waterglass of O=66.75%, weighs first
600 grams of waterglass, are added 126.5 grams of n-butylamine and solution A is made in 1181.3 grams of deionized water, are fitted into synthesis reactor,
It is stirred evenly under 300 revs/min of stirring, then weighs 41.82 grams of aluminum sulfate, merging is equipped in the beaker of 1561.4 grams of water, so
15.8 grams of sulfuric acid is added afterwards, is stirred evenly, is made in the solution that B solution is added dropwise in kettle with glass bar, then by kettle
It is closed, it is started to warm up after continuing stirring 10-20 minutes.It is small with 2 DEG C/minute of rate to rise to 120 DEG C of constant temperature 20 by room temperature for the first step
When, second step, then after being warming up to 165 DEG C with 10 DEG C/h of rate, material is drawn off and is fitted into air-tight bottle by cooling down.
B. Zeolite synthesis
Composition is as follows: SiO2∶Al2O3∶Na2O: directed agents: H2SO4: lanthanum nitrate: H2O=20: 1: 7: 2: 0.5: 0.1:
2500；
Silicon source is using composition are as follows: SiO2=25.13%；Na2O=8.12%；H2The waterglass of O=66.75%, claims first
500 grams of waterglass are taken, 1548.75 grams of deionized water is then added, C solution is made, puts it into synthesis reactor and stirs evenly,
Start to stir with 200-400 revs/min of speed, then measure the lanthanum nitrate hexahydrate 10ml of 0.1Mol/L as in E solution addition kettle,
Then the directed agents 180ml for accounting for total volume 5-10% is added, is warming up to 80 DEG C with 5 DEG C/min of rate, then weighs 69.6 again
Gram aluminum sulfate add 2218.3 grams of deionized water and 4.8 grams of sulfuric acid is configured to solution D, be added dropwise in kettle in solution,
Then kettle is closed, continue stirring and starts to warm up after ten minutes.It is small to rise to 120 DEG C of constant temperature 25 with 3 DEG C/minute of rate for the first step
When, second step, then rise to 160 DEG C of constant temperature at a slow speed 20-25 hours with 10 DEG C/h, then using after cooling water temperature, by object
Material is drawn off, and material solution is washed till pH value in 8 by precipitating filtering, is placed in furnace through 110 DEG C of drying and is roasted 5 hours at 540 DEG C
As LaZSM-5 molecular screen primary powder.
C. catalyst preparation
Above-mentioned molecular sieve is subjected to ion exchange by the hydrochloric acid solution of 0.5Mol/L, until the Na of LaZSM-5 molecular sieve+
Content < 0.1 (m) %, then drying, 500 DEG C roasting 3 hours after, obtain LaHZSM-5 molecular sieve.Then by LaHZSM-5 points
Son sieve is uniformly mixed with the weight percent of binder for 50: 50 addition binders, while molten with the dust technology of volumetric concentration 2%
After drying, catalyst is made after roasting 4 hours at 500 DEG C in liquid kneading and compacting.
2. the pre-steaming of catalyst
With the rate of 30 DEG C/h, heat cycles gas to heat catalyst according to the procedure below: being heated to 120 DEG C, constant temperature 3
Hour；It is heated to 300 DEG C, constant temperature 3 hours；It is heated to 480 DEG C, constant temperature 10 hours；
With the rate of 30 DEG C/h, by cooling catalyst to 430 DEG C, superheated steam is imported, air speed is controlled in 0.5m3·h-1,
To remove circulation air；
Using superheated steam, 460 DEG C, constant temperature 48 hours are warming up to the rate of 30 DEG C/h；
Under nitrogen circulation, cooled down with the rate of 30 DEG C/h, it is spare.
3. the preparation of hydrocarbon products
1) methanol that purity is 95% is preheated, evaporated and overheated to heat, with 12m3The liquid air speed LHSV of/h is fed
To be converted into hydrocarbon products mixture synthesis gas in insulation fix bed reactor, the reactor inlet temperature is 310 DEG C, is entered
Mouth pressure is 1.6MPa, and outlet temperature is 420 DEG C, outlet pressure 1.6MPa, and is mounted with the warp obtained in 5.2kg step 2
The catalyst of pre-steaming；
The synthesis gas of step 1) is cooled to 40 DEG C, is divided into three-phase in aromatic hydrocarbons separator: gas phase (main light component),
Liquid aqueous mixtures phase and liquid hydrocarbon phase.Gas phase returned to after recycle gas compressor compresses synthesis aromatic hydrocarbons reactor inlet with
Methanol after overheat enters synthesis aromatic hydrocarbons reactor together, and recycle ratio control is 7.5:1.
Biochemical treatment is pumped to through synthesizing aromatics process water containing some methanol, fusel aqueous mixture.Liquid hydrocarbon, that is, thick
Stable light hydrocarbon is fed directly to aromatics seperation part and is further separated into fuel gas, LPG, stable light hydrocarbon and heavy aromatics.
Under aforesaid liquid air speed, the service life of the catalyst is more than 20 days.
Embodiment 2
1. the pre-steaming of catalyst
With the rate of 30 DEG C/h, heat cycles gas to heat commercially available ZSM-5 catalyst according to the procedure below: being heated to
120 DEG C, constant temperature 2 hours；It is heated to 300 DEG C, constant temperature 3 hours；It is heated to 480 DEG C, constant temperature 8 hours；
With the rate of 30 DEG C/h, by cooling catalyst to 430 DEG C, superheated steam is imported, air speed is controlled in 0.5m3·h-1,
To remove circulation air；
Using superheated steam, 460 DEG C, constant temperature 36 hours are warming up to the rate of 30 DEG C/h；
Under nitrogen circulation, cooled down with the rate of 30 DEG C/h, it is spare.
2. the preparation of hydrocarbon products
1) methanol that purity is 98% is preheated, evaporated and overheated to heat, with 11m3The liquid air speed LHSV of/h is fed
To be converted into hydrocarbon products mixture synthesis gas in insulation fix bed reactor, the reactor inlet temperature is 315 DEG C, is entered
Mouth pressure is 1.7MPa, and outlet temperature is 400 DEG C, outlet pressure 1.7MPa, and is mounted with the warp obtained in 4.0kg step 1
The catalyst of pre-steaming；
The synthesis gas of step 1) is cooled to 45 DEG C, is divided into three-phase in aromatic hydrocarbons separator: gas phase (main light component),
Liquid aqueous mixtures phase and liquid hydrocarbon phase.Gas phase returned to after recycle gas compressor compresses synthesis aromatic hydrocarbons reactor inlet with
Methanol after overheat enters synthesis aromatic hydrocarbons reactor together, and recycle ratio control is 7.8:1.
Biochemical treatment is pumped to through synthesizing aromatics process water containing some methanol, fusel aqueous mixture.Liquid hydrocarbon, that is, thick
Stable light hydrocarbon is fed directly to aromatics seperation part and is further separated into fuel gas, LPG, stable light hydrocarbon and heavy aromatics.
Under aforesaid liquid air speed, the service life of the catalyst is more than 20 days.
The post-processing of embodiment 3:C1, C2 product
After the recovered reaction heat of hydrocarbon products mixture synthesis gas, after air cooler and cooler are cooling, in the separator
Be divided into three-phase: gas phase (predominantly light component), aqueous mixtures phase and liquid hydrocarbon phase (mainly include C2+Hydrocarbon).Gas phase is through recycling
Synthesis aromatic hydrocarbons reactor inlet is returned to after air compressor compression enters synthesis aromatic hydrocarbons reactor together with the methanol after overheat.
Biochemical treatment mutually is pumped to through synthesizing aromatics process water containing some methanol, fusel aqueous mixtures.Liquid hydrocarbon, that is, thick stable light hydrocarbon
It is fed directly to aromatics seperation part and is further separated into fuel gas, LPG, stable light hydrocarbon and heavy aromatics.
Liquefied gas knockout tower is mainly used for separating LPG from thick stable light hydrocarbon.The tower bottom product of gas removal tower is main
It is the hydro carbons of C3 or more, is further separated in liquefied gas knockout tower.Overhead product is mainly LPG, and tower bottom product is mainly C4
Above hydro carbons.Overhead product is sent into liquefied gas knockout tower return tank after total condensation, C3/C4 hydrocarbon liquid phase a part is back to
Liquefied gas knockout tower, another part is as LPG product.LPG product is sent to tank field through circulating water to 46 DEG C later.Part tower
Bottom product is pumped to absorption tower after cooler is cooling by flow control.Materials at bottom of tower enters product knockout tower and further divides
From.
Product knockout tower is fed mainly from liquefied gas knockout tower tower bottom product.Aromatics seperation is light group by product knockout tower
Divide hydrocarbon (overhead product) and heavy constituent hydrocarbon (tower bottom product).Overhead product total condensation is stable light hydrocarbon, through circulating water
After send to tank field.
For reduce in thick stable light hydrocarbon separating tank gas phase and gas removing tower overhead product low boiling component loss,
It uses partial liquefaction gas knockout tower tower bottom product stable light hydrocarbon as absorbent in absorption tower, this two bursts of gas phases is carried out at absorption
Reason.
Also parsed by absorption tower in Examples 1 and 2 through the compressed gas phase portion of recycle compressor, separation comprising C1 and
The light components of C2, the light components first pass around dehydration, then isolate carbon monoxide, carbon dioxide, C2 and C2 or more hydrocarbon
Class component drains into blow-down pipe and removes torch burning, and the methane of enrichment is sent into natural after compressor is compressed to 25MPa from 0.5MPa
Gas storage tank.
Used equipment and parameter are as shown in the table:
The reaction result for preparing hydrocarbon products according to Examples 1 and 2 is shown in table 1.
Table 1
| Embodiment | C5+Yield | LPG yield | Heavy aromatics yield |
| 1 | 36.3% | 8.5% | 2.5% |
| 2 | 36.2% | 8.6% | 2.6% |
*Wherein each product yield is based on methanol quality.
Claims (12)
1. the method for preparing hydrocarbon products by methanol by one-step method, including the following steps:
1) methanol of heating is fed in reactor to be converted into hydrocarbon products mixture synthesis gas, the reactor is mounted with
Acid Si-Al zeolite molecular sieve catalyst；
2) synthesis gas of step 1) separates liquid phase part and gas phase portion through cooling；
3) gas phase portion enters recycle compressor, and compressed at least part is mixed with material benzenemethanol as recycle stock, returned
Return reactor；Liquid phase part carries out later separation；
Acid Si-Al zeolite molecular sieve catalyst passes through pre-steaming before starting the reaction in step 1), includes the following steps:
(1) catalyst is heated to 120 DEG C, constant temperature 1~5 hour by heat cycles gas；
(2) catalyst is heated to 300 DEG C, constant temperature 1~5 hour；
(3) catalyst is heated to 480 DEG C, constant temperature 1~20 hour；
(4) by cooling catalyst to 430 DEG C, superheated steam is imported, air speed is controlled in 0.5m3·h-1, to remove circulation air；
(5) superheated steam is used, makes catalyzer temperature-elevating to 460 DEG C, constant temperature 10~60 hours；
(6) cool down under nitrogen or air circulation, it is spare；
The temperature of step 1) hydrocarbon mixture is cooled to 25~50 DEG C.
2. method described in claim 1, wherein material benzenemethanol is preheated first, evaporates and overheats, it is solid to be then fed to insulation
Fixed bed reactor.
3. method of any of claims 1 or 2, wherein catalyst is commercially available acid Si-Al zeolite molecular sieve catalyst.
4. method as claimed in claim 3, wherein the commercially available acid Si-Al zeolite molecular sieve catalyst be selected from ZSM-5,
ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-5 molecular sieve catalyst are derivative or modified
Catalyst LaHZSM-5 molecular sieve catalyst.
5. method as claimed in claim 4, wherein reactor inlet pressure is 1.5~1.8MPa；Outlet pressure be 1.5~
1.7MPa。
6. method described in claim 5, wherein reactor inlet pressure is 1.5~1.6MPa；Outlet pressure is 1.6MPa.
7. method of claim 6, wherein the liquid air speed of methanol is 0.1~80.0m3·h-1。
8. method of claim 7, wherein the liquid air speed of methanol is 50~60m3·h-1。
9. method according to any one of claims 8, wherein in step 3), through the compressed gas phase portion of recycle compressor also by absorbing
Tower parsing, separation include the light components of C1 and C2, and the light components first pass around dehydration, then isolate carbon monoxide, two
Carbonoxide, C2 and C2 or more hydrocarbon component drain into blow-down pipe and remove torch burning, and the methane of enrichment is pressed through compressor from 0.5MPa
After being reduced to 25MPa, it is sent into natural gas storage tank.
10. method as claimed in claim 9, wherein catalyst passes through pre-steaming before starting the reaction, includes the following steps:
(1) catalyst is heated to 120 DEG C, constant temperature 3 hours by heat cycles gas；
(2) catalyst is heated to 300 DEG C, constant temperature 3 hours；
(3) catalyst is heated to 480 DEG C, constant temperature 10 hours；
(4) by cooling catalyst to 430 DEG C, superheated steam is imported, air speed is controlled in 0.5m3·h-1, to remove circulation air；
(5) superheated steam is used, makes catalyzer temperature-elevating to 460 DEG C, constant temperature 48 hours；
(6) cool down under nitrogen or air circulation, it is spare.
11. method described in any one of claim 10, wherein the heating and rate of temperature fall when the catalyst pre-processes be no more than 35 DEG C/
h。
12. method described in claim 11, wherein the heating and rate of temperature fall when the catalyst pre-processes are less than 35 DEG C/h.
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