CN107790112A - For removing the activation method of oxygenatedchemicals adsorbent in low-carbon alkene - Google Patents

For removing the activation method of oxygenatedchemicals adsorbent in low-carbon alkene Download PDF

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CN107790112A
CN107790112A CN201610765550.1A CN201610765550A CN107790112A CN 107790112 A CN107790112 A CN 107790112A CN 201610765550 A CN201610765550 A CN 201610765550A CN 107790112 A CN107790112 A CN 107790112A
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adsorbent
low
temperature
oxygenatedchemicals
activation method
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CN107790112B (en
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肖永厚
洪涛
刘苏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas

Abstract

Mainly solve existing activation method the present invention relates to a kind of activation method for removing oxygenatedchemicals adsorbent in low-carbon alkene and the problems such as complex operation, activation efficiency are low, the easy coking carbon distribution of adsorbent, cause the absorption property of adsorbent to decay or even inactivate be present.The present invention is by low pressures, higher than progress ladder temperature programming under adsorption temp, the adsorbent for needing to activate solved into the problem well with the technical scheme that positive or reverse flow the high-temperature dry air with heat contacts, available for the activation method that oxygenatedchemicals adsorbent is removed in industrial low-carbon alkene.

Description

For removing the activation method of oxygenatedchemicals adsorbent in low-carbon alkene
Technical field
The present invention relates to the activation method for removing oxygenatedchemicals adsorbent in low-carbon alkene.
Background technology
The C4 resource very abundants in China, it is mainly derived from hydrocarbon cracking and refinery catalytic cracking.Isobutene contains in C4 hydrocarbon Highest is measured, and there is higher use value, its one is mainly used for reacting synthesizing methyl tertbutyl ether with methanol (MTBE).At present, most of mixing C4 is used for producing MTBE, substantial residual 1- butylene in the C4 after etherificate, simultaneously containing not anti- The oxygenatedchemicals impurity such as the methanol answered and the dimethyl ether (DME) of side reaction generation.The polarity of such impurity is stronger, it is easy to inhales The attached poisoning and deactivation for causing downstream production catalyst.To meet to produce needs, the purity requirement of C4 raw materials improves constantly, wherein H2O, the removal of the impurity such as oxygenatedchemicals such as methanol, dimethyl ether is a particularly important procedure.In numerous adsorbents, Molecular sieve has stronger polarity, abundant micropore and preferable stability, is widely used in the adsorption cleaning of various gases, liquid Process.But the single adsorptions finite capacity of molecular sieve adsorbent is, it is necessary to frequent regeneration.Such adsorbent is to things such as some alkene Matter has certain catalytic activity or adsorptivity, and the activation method of use is improper, after adsorbent repeated regeneration can be made, adsorbent Adsorption capacity declines, purification precision reduces even adsorbent rapid deactivation.
United States Patent (USP) US 4,404,118 is reported for the solid absorption after the removing oxygenatedchemicals from hydrocarbon raw material The activation method of agent.This method uses the gas dissolution adsorbent at low temperature rich in hydrogen first at less than 93.3 DEG C, then by Gradually it is warming up to the temperature generally required for regeneration.United States Patent (USP) US 6,225,518 is reported for separating alkene from alkane The activation method of adsorbent.This method includes rinsing molecular sieve with the aqueous solution containing alkali, then in the light alkane air-flow of overheat Dry.United States Patent (USP) US 2,882,244 describes X molecular sieve regeneration method, X molecular sieve can by air, vacuum, Or heating is regenerated under other atmosphere, temperature may be up to 700 DEG C, keep preferable activation effect.Another common activation Method is to substitute other adsorbates with the stronger material of adsorptivity, such as with the acetylene adsorbed on water substitution X zeolite molecular sieves.The U.S. Patent US Pat.5,245,107 are reported with liquefied gas and some isomer products to the absorption for adsorbing oxygenatedchemicals Agent carries out regeneration treatment.To prevent from generating gummy precipitation, activated alumina suitably regenerates at 177~316 DEG C, i.e., bed activates Gas minimum temperature at outlet need to maintain 177 DEG C, can recover its original absorption property.
In summary, existing adsorbent activation method, during removing polar impurity applied to low-carbon alkenes such as C4, deposit In complex operation, regeneration efficiency is low, the easy coking carbon distribution of adsorbent, causes that the absorption property of adsorbent is decayed or even inactivation etc. is asked The topic present invention is by low pressures, higher than carrying out ladder temperature programming under adsorption temp, it would be desirable to the adsorbent of activation with The technical scheme of positive or reverse flow dry gas contact solves the problem well.
The content of the invention
One of technical problems to be solved by the invention are to provide a kind of for removing oxygenatedchemicals suction in low-carbon alkene Attached dose of activation method.Existing adsorbent activating technology has that complex operation, regeneration efficiency are low, the easy coking carbon distribution of adsorbent, The problems such as causing the absorption property of adsorbent to decay or even inactivate.
To solve one of above-mentioned technical problem, this method includes following steps：
A) normal temperature purges, and is consolidated using the inert gas and/or low-carbon linear paraffin of at least one drying to what needs activated Body adsorbent carries out purging 1~6 hour at 12~48 DEG C of lower temperature；
It is desorbed in the moderate temperature stage, keeps dry activated gas to be continually fed into adsorbent bed, pass through program Adsorbent bed temperature is increased to 80~140 DEG C by heating heating with the activated gas carrying heat of drying, makes the activation of heat Gas continues through adsorbent bed, and countercurrent or cocurrent contacts with adsorbent, keeps the temperature 1~8 hour；
C) the elevated temperature desorption stage, continue to be warming up to 220~350 DEG C by adsorbent bed, and keep the temperature 1~24 small When；
D) cool down, under the protection of dry activated gas, stop heating, make adsorbent bed to be down to room Temperature.
In above-mentioned technical proposal, needed before adsorbent contacts with material to be clean by activation process.
In above-mentioned technical proposal, for removing the activation method of oxygenatedchemicals adsorbent in low-carbon alkene, its feature exists In described dry gas is selected from inert gas such as N2, at least one of He, Ar or low-carbon alkanes.Activation gas used Body is preferably dry low-carbon linear paraffin.Activated gas used is more preferably the methane gas that water content is less than 10ppm.It is living Change pressure is -0.1~3.0MPa, and activation pressure is preferably -0.1~0.2MPa, and activation pressure is more preferably normal pressure.Described use In the activation method for removing oxygenatedchemicals adsorbent in low-carbon alkene, it is characterised in that normal temperature purging temperature is in step a) 20~40 DEG C, purge 2~4 hours.Heat temperature raising temperature is to 100~130 DEG C in step b), soaking time 2~4 hours.Step C) for high temperature desorption stage warming temperature to 260~310 DEG C, soaking time is 6~20 hours.It is described to be used to remove low-carbon alkene The activation method of oxygenatedchemicals adsorbent in hydrocarbon, it is characterised in that the volume space velocity of activated gas is 100~5000 hours-1。 The described activation method for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, it is characterised in that the volume of activated gas Air speed is 200~800 hours-1。
Adsorbent activation method of the present invention, it is simple to operate by the activation method of ladder temperature programming, after activation The absorption property of adsorbent reaches or close to optimum activity, while avoids coking, carbon distribution.Molecular sieve adsorbent was adsorbing Cheng Zhong, stronger electric field is formed around metal ion, generates powerful electrostatic attraction.These characteristics have zeolite molecular sieve Good absorption property, while adsorbing and removing polarity is compared with strong impurity, substantial amounts of hydrocarbons are inevitably adsorbed.
The present invention provides a kind of activation method of ladder temperature programming, and this method is simple to operate, regeneration efficiency is high, avoids Adsorbent coking carbon distribution.
Using activation method provided by the invention, first, urged sweeping by activated gas at a lower temperature, make to remain in suction Olefin compound removing in attached dose of surface or duct；Using the method for ladder-elevating temperature, adsorbent surface can be effectively controlled The desorption rate of institute's adsorbing contaminant and hydrocarbon, diffusion velocity and desorption rate are effectively matched, so as to slow down in desorption process The aggregation of impurity or remaining hydro carbons, acid-base property and structural damage effect to molecular sieve adsorbent surface.In activation Incipient stage, the residuals of adsorbent surface are more, and need to only depressurize purging just has substantial amounts of material to be desorbed, with desorption Progress surface mass desorption rate and desorption rate reduce simultaneously, the method for now taking progressively ladder-elevating temperature, pass through optimization Programming rate can effectively control desorption rate, and match well with diffusion velocity, so as to reach preferable activation effect Fruit.The formation speed of accessory substance is controlled, effectively reduces the possibility that the material forms polymer.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts with C4 hydrocarbon materials to be clean by activation process.Activation process and actual conditions For：Activate the gases used CH for being less than 10ppm for water content4Gas, first at 30 DEG C of room temperature, in constant N2The tolerance of gas For 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, under normal pressure, purging is located at the adsorbent in absorber, purging Time is 2 hours.Then, it is CH to switch regeneration gas4Gas, 130 DEG C are warming up to 2 DEG C/min speed program, and kept Temperature 3 hours, make the partial impurities desorption adsorbed in adsorbent surface and duct, continue the speed program heating with 5 DEG C/min To 300 DEG C, the temperature is kept 6 hours, then, in CH4Under gas shield, the absorption after being activated after carrying out cooling 2 hours Agent AC-1, is cooled to about 30 DEG C of room temperature, while by CH4Gas switches to low-carbon alkene to be clean, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Embodiment 2】
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts with C4 hydrocarbon materials to be clean by activation process.Activation process and actual conditions For：Activate the gases used N for being less than 10ppm for water content2Gas, first at 30 DEG C of room temperature, in the tolerance of constant Ar gases For 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, under normal pressure, purging is located at the adsorbent in absorber, purging Time is 2 hours.Then it is the N that water content is less than 10ppm to switch regeneration gas2Gas, it is warming up to 2 DEG C/min speed program 130 DEG C, and keeping temperature 3 hours, make the partial impurities desorption adsorbed in adsorbent surface and duct, continue with 5 DEG C/min Speed program be warming up to 300 DEG C, the temperature is kept 6 hours, then, in dry N2Under protection, obtained after carrying out cooling 2 hours Adsorbent A C-2 after to activation, is cooled to about 30 DEG C of room temperature, while by N2Low-carbon alkene is switched to, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Embodiment 3】
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts with C4 hydrocarbon materials to be clean by activation process.Activation process and actual conditions For：The gases used Ar gases for being less than 10ppm for water content are activated, first at 30 DEG C of room temperature, in the tolerance of constant Ar gases For 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, under normal pressure, purging is located at the adsorbent in absorber, purging Time is 2 hours, is then warming up to 130 DEG C with 2 DEG C/min speed program, and keeping temperature 3 hours, makes adsorbent surface Partial impurities desorption with being adsorbed in duct, continues to be warming up to 300 DEG C with 5 DEG C/min speed program, keeps the temperature 6 small When, then, under Ar protections, the adsorbent A C-3 after being activated after carrying out cooling 2 hours, about 30 DEG C of room temperature is cooled to, together When Ar switched into low-carbon alkene, carry out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Embodiment 4】
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts with C4 hydrocarbon materials to be clean by activation process.Activation process and actual conditions For：The gases used He gases for being less than 10ppm for water content are activated, first at 30 DEG C of room temperature, in the tolerance of constant He gases For 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, under normal pressure, purging is located at the adsorbent in absorber, purging Time is 2 hours, is then warming up to 130 DEG C with 2 DEG C/min speed program, and keeping temperature 3 hours, makes adsorbent surface Partial impurities desorption with being adsorbed in duct, continues to be warming up to 300 DEG C with 5 DEG C/min speed program, keeps the temperature 6 small When, then, under He protections, the adsorbent A C-4 after being activated after carrying out cooling 2 hours, about 30 DEG C of room temperature is cooled to, together When He switched into low-carbon alkene, carry out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Embodiment 5】
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts with C4 hydrocarbon materials to be clean by activation process.Activation process and actual conditions For：It is that volume content of the water content less than 10ppm is 50%CH to activate gases used4And 50%N2Mixed gas, first in room temperature It is 20ml/min in the tolerance of constant above-mentioned mixed inert gas, i.e., gas volume air speed is 600h at 30 DEG C-1Condition Under, under normal pressure, purging is located at the adsorbent in absorber, and purge time is 2 hours, then with 2 DEG C/min speed program liter Temperature is to 130 DEG C, and keeping temperature 3 hours, and the partial impurities for making to adsorb adsorbent surface and duct in are desorbed, continue with 5 DEG C/ Min speed program is warming up to 300 DEG C, keeps the temperature 6 hours, then, under mixed inert gas protection, carries out cooling 2 Adsorbent A C-5 after being activated after hour, is cooled to about 30 DEG C of room temperature, while mixed inert gas are switched into low-carbon alkene Hydrocarbon, carry out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Embodiment 6-18】
Adsorbent and imurity-removal system used is same as Example 1.Only change the gaseous species, flow, gas of activation The parameters such as body volume space velocity, the temperature of temperature programming, programming rate and time.Specific activation condition change refers to table 1.
Table 1
【Comparative example 1】
From adsorbent same as Example 1, using identical appreciation condition, it is used in adsorbent in removing mixing C4 After DME, simply change activation method and only save a) step, other steps are constant.Using appreciation condition same as Example 1, Appraisal result is given in Table 2.Detailed process is as follows：
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Activate the gases used CH for being less than 10ppm for water content4Gas, first at ambient pressure, in constant CH4The gas of gas Measure as 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, purging is located at the adsorbent in absorber, with 2 DEG C/min Speed program be warming up to 130 DEG C, and keeping temperature 3 hours, the partial impurities for making to adsorb in adsorbent surface and duct take off It is attached, continue to be warming up to 300 DEG C with 5 DEG C/min speed program, keep the temperature 6 hours, then, in CH4Under gas shield, enter Row cooling activated after 2 hours after adsorbent B -1, be cooled to about 30 DEG C of room temperature, while by CH4Gas switches to low-carbon alkene Hydrocarbon, carry out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Comparative example 2】
From adsorbent same as Example 1, using identical appreciation condition, it is used in adsorbent in removing mixing C4 After DME, simply change activation method and save b) step, other steps are constant.Using appreciation condition same as Example 1, examine Result is commented to be given in Table 2.Detailed process is as follows：
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Activate the gases used CH for being less than 10ppm for water content4Gas, first at 30 DEG C of room temperature, in constant CH4Gas Tolerance be 20ml/min, i.e., gas volume air speed is 600h-1Under conditions of, under normal pressure, purging is located at the absorption in absorber Agent, purge time are 2 hours, are then warming up to 300 DEG C with 5 DEG C/min speed program, keep the temperature 6 hours, then, CH4Under gas shield, adsorbent B -2 after being activated after carrying out cooling 2 hours, about 30 DEG C of room temperature is cooled to, while by CH4 Gas switches to low-carbon alkene, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Comparative example 3】
From adsorbent same as Example 1, using identical appreciation condition, it is used in adsorbent in removing mixing C4 After DME, simply change activation method and save c) step, other steps are constant.Using appreciation condition same as Example 1, examine Result is commented to be given in Table 2.Detailed process is as follows：
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Activate the gases used CH for being less than 10ppm for water content4Gas, first at ambient pressure, in constant CH4The gas of gas Measure as 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, purging is located at the adsorbent in absorber, with 2 DEG C/min Speed program be warming up to 130 DEG C, and keeping temperature 3 hours, the partial impurities for making to adsorb in adsorbent surface and duct take off It is attached, then, in CH4Under gas shield, adsorbent B -3 after being activated after carrying out cooling 2 hours, room temperature about 30 is cooled to DEG C, while by CH4Gas switches to low-carbon alkene, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Comparative example 4】
From adsorbent same as Example 1, using identical appreciation condition, it is used in adsorbent in removing mixing C4 After DME, simply change activation method and save d) step, other steps are constant.Using appreciation condition same as Example 1, examine Result is commented to be given in Table 2.Detailed process is as follows：
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Activate the gases used CH for being less than 10ppm for water content4Gas, first at ambient pressure, in constant CH4The gas of gas Measure as 20ml/min, i.e. gas volume air speed is 600h-1Under conditions of, purging is located at the adsorbent in absorber, with 2 DEG C/min Speed program be warming up to 130 DEG C, and keeping temperature 3 hours, the partial impurities for making to adsorb in adsorbent surface and duct take off It is attached, continue to be warming up to 300 DEG C with 5 DEG C/min speed program, keep the temperature 6 hours, adsorbent B -4 after being activated, Simultaneously by CH4Gas switches to low-carbon alkene, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Comparative example 5】
From adsorbent same as Example 1, using identical appreciation condition, it is used in adsorbent in removing mixing C4 After DME, simply change the CH that inert gas used in activation method exceedes 20ppm for water content4, other steps are constant.Adopt With appreciation condition same as Example 1, appraisal result is given in Table 2.Detailed process is as follows：
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts after adsorption experiment with C4 hydrocarbon materials to be clean by activation process.Activated Journey and actual conditions are：Activate the gases used CH for being higher than 20ppm for water content4Gas, first at 30 DEG C of room temperature, constant CH4The tolerance of gas is 20ml/min, i.e., gas volume air speed is 600h-1Under conditions of, under normal pressure, purging is located in absorber Adsorbent, purge time be 2 hours, be then warming up to 130 DEG C with 2 DEG C/min speed program, and keeping temperature 3 is small When, make the partial impurities desorption adsorbed in adsorbent surface and duct, continue to be warming up to 300 DEG C with 5 DEG C/min speed program, The temperature is kept 6 hours, then, in CH4Under gas shield, adsorbent B -5 after being activated after carrying out cooling 2 hours, drop Warm to room temperature about 30 DEG C, while by CH4Gas switches to low-carbon alkene, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
【Comparative example 6】
From adsorbent same as Example 1, using identical appreciation condition, it is used in adsorbent in removing mixing C4 After DME, the operating pressure simply changed when being activated in activation method is 3.0MPa, and other steps are constant.Using with the phase of embodiment 1 Same appreciation condition, appraisal result are given in Table 2.Detailed process is as follows：
The solid absorbent used in the present invention is using Zn2+The Y type molecular sieve of ion-exchanged, for from mixing C4 Adsorbing and removing oxygenatedchemicals in hydrocarbon.Spy of the experiment using the dimethyl ether in C4 hydrocarbon streams as oxygenatedchemicals impurity to be removed Pin molecule.Based on the gross weight of provided C4 hydrocarbon streams, the content of dimethyl ether is 150ppmw.The adsorption assessment condition is： 2.0MPa, at 35 DEG C, 2h-1Liquid volume air speed, the loadings of adsorbent are 2ml, and the exterior appearance of adsorbent is straight for particle Footpath size is the cylindrical particle of 10~20 mesh.
Needed before adsorbent contacts after adsorption experiment with C4 hydrocarbon materials to be clean by activation process.Activated Journey and actual conditions are：Activate the gases used CH for being less than 10ppm for water content4Gas, first at 30 DEG C of room temperature, constant CH4The tolerance of gas is 20ml/min, i.e., gas volume air speed is 600h-1Under conditions of, in the case where pressure is 3.0MPa, purge position Adsorbent in absorber, purge time are 2 hours, are then warming up to 130 DEG C with 2 DEG C/min speed program, and protect Hold temperature 3 hours, make the partial impurities desorption adsorbed in adsorbent surface and duct, continue the speed program liter with 5 DEG C/min Temperature keeps the temperature 6 hours, then, in CH to 300 DEG C4Under gas shield, the suction after being activated after carrying out cooling 2 hours Attached dose of B-6, is cooled to about 30 DEG C of room temperature, while by CH4Gas switches to low-carbon alkene, carries out adsorption experiment.
It is as follows to the appreciation condition of adsorbent after activation：At 2.0MPa, 35 DEG C, 2h-1Liquid volume air speed, adsorbent Loadings be 2ml, the exterior appearance of adsorbent is the cylindrical particle that particle diameter size is 10~20 mesh.
Table 2 gives absorption property corresponding to Different Activation Methods, and above-mentioned evaluation result is shown in Table 2.
Table 2
As seen from Table 2, with activation method provided by the invention, avoid directly under the high temperature conditions, the knot of such material Burnt, carbon distribution.Using the method for ladder-elevating temperature, the activity of adsorbent, the important technology index such as adsorbance and equilibrium adsorption capacity is penetrated It is preferably horizontal, achieve preferable technique effect.

Claims (10)

1. a kind of activation method for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, this method include following step Suddenly：
A) normal temperature purges, and the solid that needs activate is inhaled using the inert gas and/or low-carbon linear paraffin of at least one drying Attached dose at 12~48 DEG C of lower temperature, carries out purging 1~6 hour；
B) it is desorbed in the moderate temperature stage, keeps dry activated gas to be continually fed into adsorbent bed, pass through program liter Adsorbent bed temperature is increased to 80~140 DEG C by temperature heating with the activated gas carrying heat of drying, makes the activation gas of heat Body continues through adsorbent bed, and countercurrent or cocurrent contacts with adsorbent, keeps the temperature 1~8 hour；
C) the elevated temperature desorption stage, continue to be warming up to 220~350 DEG C by adsorbent bed, and keep the temperature 1~24 hour；
D) cool down, under the protection of dry activated gas, stop heating, make adsorbent bed to be down to room temperature.
2. the activation method according to claim 1 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature It is that the inert gas of above-mentioned drying is selected from N2, at least one of He, Ar.
3. the activation method according to claim 1 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature The activated gas for being drying used is dry low-carbon linear paraffin.
4. it is used for the activation method for removing oxygenatedchemicals adsorbent in low-carbon alkene according to claim 3, it is characterised in that institute The activated gas of drying is the methane gas that water content is less than 10ppm.
5. it is used for the activation method for removing oxygenatedchemicals adsorbent in low-carbon alkene according to claim 1, it is characterised in that living Change pressure is -0.1~3.0MPa.
6. the activation method according to claim 5 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature It is -0.1~0.2MPa to be activation pressure.
7. the activation method according to claim 5 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature It is normal pressure to be activation pressure.
8. the activation method according to claim 1 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature It is in step a) that normal temperature purging temperature is 20~40 DEG C, is purged 2~4 hours.
9. the activation method according to claim 1 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature It is in step b) heat temperature raising temperature to 100~130 DEG C, soaking time 2~4 hours.
10. the activation method according to claim 1 for being used to remove oxygenatedchemicals adsorbent in low-carbon alkene, its feature It is step c) high temperature desorption stage warming temperatures to 260~310 DEG C, soaking time is 6~20 hours.
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