CN107999020A - A kind of preparation method of Woelm Alumina dealcoholysis agent - Google Patents
A kind of preparation method of Woelm Alumina dealcoholysis agent Download PDFInfo
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- CN107999020A CN107999020A CN201711194833.6A CN201711194833A CN107999020A CN 107999020 A CN107999020 A CN 107999020A CN 201711194833 A CN201711194833 A CN 201711194833A CN 107999020 A CN107999020 A CN 107999020A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
The invention discloses a kind of preparation method of Woelm Alumina dealcoholysis agent, Woelm Alumina dealcoholysis agent specific surface area prepared by the present invention generally can reach 400m2/ more than g, pore volume are more than 0.5cm3/ g, duct are mesoporous for 5~13nm slit-types.Adsorption reaction is suitable for different process conditions, especially also has the higher adsorption capacity that penetrates at normal temperatures and pressures, and general more than 8%, saturated adsorption capacity is up to more than 25%；It is high to remove precision, can directly be removed to below 0.1ppm；Regeneration temperature is 100~300 DEG C, and reproduction speed is fast；Reaction rate is fast, can bear larger space velocity range, nontoxic, without side reaction, no coupling product, and multiple absorption regeneration recycles performance and declines unobvious, has preferable cyclical stability, environmental nonpollution corrosion-free to equipment.
Description
Technical field
The present invention relates to environmental protection and chemical technology field, more particularly to a kind of preparation method of Woelm Alumina dealcoholysis agent.
Background technology
Ethene, propylene are most important basic organic chemical raw materials, and wherein ethylene industry is even more to weigh a National Industrial
The mark of petrochemical industry level.The ethene in China, propylene industry are developed rapidly in recent years, but since China is special
The energy resource structure of different " rich coal, oil starvation, few gas ", causes ethene, propylene production capacity to be unable to meet demand for a long time, this is coal-to-olefin
Provide wide space.Producing the production stage of lower carbon number hydrocarbons through methanol using coal as raw material mainly includes：Producing synthesis gas from coal, synthesis
Four purification of gas, gas methanol, methanol-to-olefins steps.The lower carbon number hydrocarbons produced obtains production by separation, purification and gathers
The unstripped gas of alkene, can still contain in the ethene of these polymer grades, propylene feedstocks gas and its micro methanol, dimethyl ether, propionic aldehyde
Isopolarity foreign gas, these oxygen containing foreign gases will cause catalyst poisoning to inactivate when synthesizing product downstream, drop
The selectivity of low catalyst, the conversion ratio in turn resulting in reaction declines, influences a series of problems, such as product quality, thus must take off
Except the stable operation that just can guarantee that device to below 1ppm.Mesoporous in porous material can optionally accommodate guest molecule,
Possessed high-specific surface area is conducive to gas molecule absorption, and Woelm Alumina dealcoholysis agent utilizes the adsorption theory of porous material
Absorption to making choice property of target substance, has that precision is high, capacity is big, technique is simple, cycle performance is excellent, of low cost etc.
Feature, therefore porous oxidation aluminum is used in the removing of Trace Methanol by as the ideal path of dry method depth dealcoholysis.
Patent document：CN104190352A discloses a kind of absorption for being used to remove sulfur-bearing, oxygen impurities in light hydrocarbon materials stream
Agent and its renovation process is prepared, activated alumina and kaolin are carried out reaming by the method via organic amine, add a small amount of alkali afterwards
Metal salt solution and binding agent carry out mixing balling-up, then adsorbent is made by low temperature drying, high-temperature calcination；Patent document：
CN106423114 A disclose preparation method and the application of a kind of hydrocarbon impurities purifying adsorbent, this adsorbent is by molecular sieve 35-
59%th, rare earth oxide 0.5-1%, aluminium oxide 40-64% are formed, and add the adhesive of 15-20%, mechanical agitation mixing,
Be granulated, be dry, adsorbent is made in activation, the impurity such as alcohol, ether, carbon dioxide and water in hydrocarbon raw material can be removed；Patent document：
CN105585405 A disclose a kind of method using discarded SAPO-34 molecular sieve catalyst adsorbing and removing methanol, and this method will
Discarded SAPO-34 molecular sieves carry out high temperature regeneration, afterwards with a certain amount of aluminium oxide, silica, phosphorus pentoxide, sodium oxide molybdena,
Potassium oxide etc. solid powder mixed-forming, is made adsorbent, specific surface area>100m2/ g, pore volume>0.05cm3/ g, for C2-
C6The removing of the oxygenate impurity such as methanol in olefin feedstock.Absorption is made using the method directly mixed in above-mentioned three classes adsorbent
Agent, although such adsorbent preparation process is relatively easy, exist mix it is uneven so as to cause or avtive spot distribution not
A series of problems, such as, influences the rate of adsorption and effect.
Patent document：CN102921373 A disclose one kind with zeolite molecular sieve, activated alumina and metal oxide
For raw material, the methods of using fabricated in situ, ion exchange, the synthesis zeolite on activated alumina, then pass through infusion process
By metal oxide supported on carrier, so that the method for adsorbent be made.Patent document：CN105289477 A disclose one
The adsorbent of imurity-removal and its application in kind of coal chemical industry olefin stream, by zeolite molecular sieve, mesoporous material, metal component according to
Certain proportion mixed-forming, rear add in metal or metal oxide solution carry out impregnating obtained adsorbent；And patent document：
A kind of method of adsorption cleaning hydrocarbon material flow, patent document disclosed in CN101885656 A：It is a kind of disclosed in CN104148006A
Remove the adsorbent and its preparation, renovation process of polar molecule in light hydrocarbon materials stream；Above-mentioned four kinds of adsorbents are using dipping
Method load active component, direct dipping process easily cause duct blockage problem, so as to cause its decarburization activity to substantially reduce, are catalyzed
The utilization rate of agent declines, and since load capacity is unable to control, and then bringing regeneration difficult, reaction rate decline etc. can not be ignored
The problem of.
Patent document CN104383874A discloses a kind of purifying adsorbent based on meso-porous molecular sieve material and its preparation
Methods and applications, this method is by mechanical agitation mixing, granulation, the roasting according to a certain percentage of mesopore molecular sieve, activated alumina
Carrier is made, using the method carried metal component of spray, adsorbent, the adsorbable second of the adsorbent is made by dry activate
The foreign gases such as the carbon dioxide that is included in the logistics such as alkene, propylene, butylene, water, oxygen, alcohol, ether；Patent document
CN103495378A discloses a kind of alkene purifying adsorbent and its method for alkene purification technique, and this method is with kaolin
35-50%, binding agent 20-30%, submicron molecular sieve 30-40%, mechanical mixture is uniform, after be put into bowling machine and spray into sodium salt
Solution is granulated, and the impurity such as adsorbent, the main methanol absorbed in alkene, dimethyl ether, propionic aldehyde is being made by dry, roasting；On
Two kinds of adsorbents are stated using molecular sieve as main carriers component, the load active component by the way of spray, such method is ignored
Load active component is easy to cause active component uneven in a manner of spraying or spray, and even only rests on table
Face, can not be deep into the inside of carrier, so bring active component content it is relatively low caused by capacity it is small the problem of.
The content of the invention
Strong it is an object of the present invention to provide a kind of high accuracy, large capacity, high-ratio surface, pore structure prosperity, cyclical stability
The preparation method of Woelm Alumina dealcoholysis agent.
To achieve the above object, the technical scheme is that：
1st, Al is selected3+As the source of main carrier component, polyethylene glycol is added as expanding agent, is configured to mixed solution,
It is saline and alkaline than being 1 using organic amine as precipitating reagent:(1.3~3.5), using direct precipitation method, in the churned mechanically bar of heating water bath
Aluminium glue body is obtained under part, and colloid is aged to stable state, obtains colloid A.
2nd, 5~15% alkaline metal salts are added into step 1 gained colloid A to fill as coagent, heating water bath, stirring
Divide reaction, control 7<PH<10, obtain mixed sediment B.Aluminium glue body is obtained, through centrifuge washing, in the case where temperature is 80~120 DEG C
Drying, through the roasting of 400~700 DEG C of Muffle furnace, after be ground into the powder that particle diameter is less than 200 mesh, obtain active oxidation aluminium powder.
3rd, active oxidation aluminium powder made from step 2 is added into a certain proportion of molecular sieve, binding agent, expanding agent, in double spiral shells
Revolve in cone-type mixer and be uniformly mixed, the spherical of 1~3mm of diameter, rear sealing, moisturizing are prepared under 20~30% damp condition
Curing is fired up to Woelm Alumina dealcoholysis agent to stabilization, then through Muffle furnace in baking oven.
Al described in step 13+The Component Source of main carrier is mainly one kind or several in aluminium chloride, aluminum nitrate, aluminum sulfate
The mixture of kind, aluminium salt mass concentration are 5~30%；For the molecular weight polyethylene glycol between 300-700, addition accounts for master
The 1-10% of carrier.
Organic amine described in step 1 is hydramine (MEA, DEA, TEA, DIPA, MDEA), enamine (DETA, TETA, TEPA)
Deng any one or a few the mixture in organic amine, preferably DEA, MEA, TEA, DETA, TETA, its concentration for 5~
30wt%.
Water bath heating temperature described in step 1 is 20~100 DEG C, is preferably 60~80 DEG C, mixing speed for 300~
700r/min, reaction time are 0.5~3h.
The Aging Temperature of composite colloid A described in step 1 is consistent with reaction temperature, and digestion time is 24~48h.
Alkaline metal salt described in step 2 is mainly the one or more member in lithium (Li), sodium (Na), potassium (K), rubidium (Rb)
One or more of mixtures in the carbonate or bicarbonate of element.
Centrifuge washing condition described in step 2 is washes twice, and alcohol is washed twice.
Molecular sieve described in step 3 is mainly one or more of mixtures in A types, X-type, Y type molecular sieve, additive amount
For 10-50%, the binding agent is calcium oxide, one or more of mixtures in bentonite, kaolin, waterglass, addition
Measure as 1-10%, the expanding agent is mainly sesbania powder, additive amount 1-10%.
Cooking conditions described in step 3 heat 12-24h, the roasting condition, with 10 DEG C/min for 50-150 DEG C for baking oven
Speed, 400~700 DEG C of temperature, temperature programmed control fire 4-12h.
The positive effect of the present invention is：
1st, used silicon source is inorganic aluminate cheap and easy to get, and preparation condition is gentle；
2nd, there is following clear superiority by the use of organic amine as precipitating reagent and template：
(1) alkalescence of organic amine belongs to weak base, and slowly ionization, alkalescence are gentle in aqueous so that precipitation reaction is orderly
Occur.
(2) organic amine often can be miscible with arbitrary proportion with water, and solubility is very big, this had both improved the throwing of unit interval
Doses, also facilitates the washing and post processing of product, reduces cost；
(3) organic amine plays multiple action in the reaction, is both precipitating reagent and dispersant, or template, this is
Prepare prosperity pore passage structure, higher ratio surface, relatively narrow pore-size distribution, high degree of dispersion activated centre active oxidation
Aluminium provides the foundation；
3rd, abundant duct knot is provided for dealcoholysis agent as main duct auxiliary agent using A types, X-type, Y type molecular sieve
Structure, improves specific surface area, so as to substantially increase adsorption capacity；
4th, the present invention is directly heavy using aluminium chloride, aluminum nitrate, one or more of mixture in aluminum sulfate and organic amine
Shallow lake prepares aluminium glue body, and then by the use of alkali metal salt as coagent, directly mixing mixes as a solution, compared to common blending
The adsorbent that method, infusion process, spray-on process obtain wants higher than surface, and pore-size distribution is more homogeneous, and avtive spot is more rich, in activity
The heart is more dispersed, and the synergistic effect between main active component and various auxiliary agents is more obvious, the utilization rate higher of active component；
5th, dealcoholysis agent of the invention, specific surface area generally can reach 400m2/ more than g, pore volume are more than 0.5cm3/ g, duct
It is mesoporous for 5~13nm slit-types.Adsorption reaction is suitable for different process conditions, especially also has at normal temperatures and pressures higher
Penetrate adsorption capacity, general up to more than 18%, saturated adsorption capacity is up to more than 25%；It is high to remove precision, can directly take off
Except to below 0.1ppm；Regeneration temperature is 100~300 DEG C, and reproduction speed is fast；Reaction rate is fast, can bear larger air speed model
Enclose, nontoxic, without side reaction, no coupling product, multiple adsorption-regeneration cycles performance declines unobvious, has preferable circulation
Stability, environmental nonpollution corrosion-free to equipment.
Brief description of the drawings
Attached drawing 1 is dealcoholysis agent evaluation rubric figure.
Attached drawing 2 is dealcoholysis agent SABET isothermals inhale (de-) attached curve map.
Attached drawing 3 is dealcoholysis agent SABJH method pore size distribution curve figures.
Attached drawing 4 is dealcoholysis agent SAXRD spectra.
Embodiment
Clear, complete description is further carried out to technical scheme with reference to embodiment.If without spy
The conventional means bright, technological means used is well known to the skilled person in following embodiments are not mentionleted alone.
Embodiment 1
1st, the AlCl of 0.5mol is weighed3.6H2O, 0.02mol polyethylene glycol 400, are configured to AlCl3.6H2O mass fractions are
10% solution A, is poured into 500mL three-necked flasks, spare；
2nd, 0.2mol diethylenetriamines (DETA) are weighed again, are configured to the lye B that mass fraction is 10%, it is spare；
3rd, the three-necked flask equipped with Aluminium chloride hexahydrate solution A is placed in 80 DEG C of water-bath, opens stirring 800r/
Min, lye B is added dropwise into Aluminium chloride hexahydrate solution A with constant pressure funnel, and time for adding control is in 1h or so, control
System 7.5<pH<8.5；
4th, after follow-up continuous insulated and stirred 1h is added dropwise to complete stop reaction, obtain alumina gel, by the colloid of acquisition in
18h is aged under reaction temperature；
5th, after the completion of to be aged, 5% NaHCO is added3, 800r/min stirring reaction 10min, by the precipitation obtained from
The heart separates, and is washed twice respectively with water and ethanol, keeps 7<PH<10, it is centrifugally separating to obtain compound alumine hydroxide colloid C；
6th, colloid C is placed in 85 DEG C of oven for drying, and is placed on 500 DEG C of temperature programmed control roasting 2h in Muffle furnace and is aoxidized
Aluminium D；
7th, aluminium oxide D is ground into powder of the particle diameter less than 200 mesh, adds 45%13X, 55%4A molecular sieve, 1% oxygen
Change calcium, 1-3h is mixed in double-spiral conical mixer, obtains uniformly mixed powder E；
8th, uniformly mixed dry powder E is taken out, is put into bowling machine, the balling-up under 20% damp condition, then sealing is put
100 DEG C of baking oven curing 18h are placed in, then is made through 650 DEG C of progress temperature programmed control roastings of Muffle furnace and Woelm Alumina dealcoholysis is made
Agent SA。
Embodiment 2
1st, the AlCl of 0.5mol is weighed3.6H2O, 0.02mol polyethylene glycol 400, are configured to AlCl3.6H2O mass fractions are
10% solution A, is poured into 500mL three-necked flasks, spare；
2nd, 0.2mol monoethanolamines (MEA) are weighed again, are configured to the lye B that mass fraction is 10%, it is spare；
3rd, the three-necked flask equipped with Aluminium chloride hexahydrate solution A is placed in 80 DEG C of water-bath, opens stirring 800r/
Min, lye B is added dropwise into Aluminium chloride hexahydrate solution A with constant pressure funnel, and time for adding control is in 1h or so, control
System 7.5<pH<8.5；
4th, after follow-up continuous insulated and stirred 1h is added dropwise to complete stop reaction, obtain alumina gel, by the colloid of acquisition in
18h is aged under reaction temperature；
5th, after the completion of to be aged, 5% NaHCO is added3, 800r/min stirring reaction 10min, by the precipitation obtained from
The heart separates, and is washed twice respectively with water and ethanol, keeps 7<PH<10, it is centrifugally separating to obtain compound alumine hydroxide colloid C；
6th, colloid C is placed in 85 DEG C of oven for drying, and is placed on 500 DEG C of temperature programmed control roasting 2h in Muffle furnace and is aoxidized
Aluminium D；
7th, aluminium oxide D is ground into powder of the particle diameter less than 200 mesh, adds 55%13X, 45%5A molecular sieve, 1% height
Ridge soil is used as binding agent, and 1-3h is mixed in double-spiral conical mixer, obtains uniformly mixed powder E；
8th, uniformly mixed dry powder E is taken out, is put into bowling machine, the balling-up under 20% damp condition, then sealing is put
100 DEG C of baking oven curing 18h are placed in, then is made through 650 DEG C of progress temperature programmed control roastings of Muffle furnace and Woelm Alumina dealcoholysis is made
Agent SB。
Embodiment 3
1st, the AlCl of 0.5mol is weighed3.6H2O, 0.02mol polyethylene glycol 400, are configured to AlCl3.6H2O mass fractions are
10% solution A, is poured into 500mL three-necked flasks, spare；
2nd, 0.2mol triethanolamines (TEOA) are weighed again, are configured to the lye B that mass fraction is 10%, it is spare；
3rd, the three-necked flask equipped with Aluminium chloride hexahydrate solution A is placed in 80 DEG C of water-bath, opens stirring 800r/
Min, lye B is added dropwise into Aluminium chloride hexahydrate solution A with constant pressure funnel, and time for adding control is in 1h or so, control
System 7.5<pH<8.5；
4th, after follow-up continuous insulated and stirred 1h is added dropwise to complete stop reaction, obtain alumina gel, by the colloid of acquisition in
18h is aged under reaction temperature；
5th, after the completion of to be aged, 5% NaHCO is added3, 800r/min stirring reaction 10min, by the precipitation obtained from
The heart separates, and is washed twice respectively with water and ethanol, keeps 7<PH<10, it is centrifugally separating to obtain compound alumine hydroxide colloid C；
6th, colloid C is placed in 85 DEG C of oven for drying, and is placed on 500 DEG C of temperature programmed control roasting 2h in Muffle furnace and is aoxidized
Aluminium D；
7th, by aluminium oxide D be ground into particle diameter be less than 200 mesh powder, add 50%13X molecular sieves, 1% bentonite,
Mixing 1-3h, obtains uniformly mixed powder E in double-spiral conical mixer；
8th, uniformly mixed dry powder E is taken out, is put into bowling machine, the balling-up under 20% damp condition, then sealing is put
100 DEG C of baking oven curing 18h are placed in, then is made through 650 DEG C of progress temperature programmed control roastings of Muffle furnace and Woelm Alumina dealcoholysis is made
Agent SC。
Embodiment 4
1st, the AlCl of 0.5mol is weighed3.6H2O, 0.02mol polyethylene glycol 400, are configured to AlCl3.6H2O mass fractions are
10% solution A, is poured into 500mL three-necked flasks, spare；
2nd, 0.2mol diethanol amine (DEA) is weighed again, is configured to the lye B that mass fraction is 10%, it is spare；
3rd, the three-necked flask equipped with Aluminium chloride hexahydrate solution A is placed in 80 DEG C of water-bath, opens stirring 800r/
Min, lye B is added dropwise into Aluminium chloride hexahydrate solution A with constant pressure funnel, and time for adding control is in 1h or so, control
System 7.5<pH<8.5；
4th, after follow-up continuous insulated and stirred 1h is added dropwise to complete stop reaction, obtain alumina gel, by the colloid of acquisition in
18h is aged under reaction temperature；
5th, after the completion of to be aged, 5% NaHCO is added3, 800r/min stirring reaction 10min, by the precipitation obtained from
The heart separates, and is washed twice respectively with water and ethanol, keeps 7<PH<10, it is centrifugally separating to obtain compound alumine hydroxide colloid C；
6th, colloid C is placed in 85 DEG C of oven for drying, and is placed on 500 DEG C of temperature programmed control roasting 2h in Muffle furnace and is aoxidized
Aluminium D；
7th, by aluminium oxide D be ground into particle diameter be less than 200 mesh powder, add 50%4A molecular sieves, 1% calcium oxide,
Mixing 1-3h, obtains uniformly mixed powder E in double-spiral conical mixer；
8th, uniformly mixed dry powder E is taken out, is put into bowling machine, the balling-up under 20% damp condition, then sealing is put
100 DEG C of baking oven curing 18h are placed in, then is made through 650 DEG C of progress temperature programmed control roastings of Muffle furnace and Woelm Alumina dealcoholysis is made
Agent SD。
Embodiment 5
1st, the AlCl of 0.5mol is weighed3.6H2O, 0.02mol polyethylene glycol 400, are configured to AlCl3.6H2O mass fractions are
10% solution A, is poured into 500mL three-necked flasks, spare；
2nd, 0.2mol triethylene tetramines (TETA) are weighed again, are configured to the lye B that mass fraction is 10%, it is spare；
3rd, the three-necked flask equipped with Aluminium chloride hexahydrate solution A is placed in 80 DEG C of water-bath, opens stirring 800r/
Min, lye B is added dropwise into Aluminium chloride hexahydrate solution A with constant pressure funnel, and time for adding control is in 1h or so, control
System 7.5<pH<8.5；
4th, after follow-up continuous insulated and stirred 1h is added dropwise to complete stop reaction, obtain alumina gel, by the colloid of acquisition in
18h is aged under reaction temperature；
5th, after the completion of to be aged, 5% NaHCO is added3, 800r/min stirring reaction 10min, by the precipitation obtained from
The heart separates, and is washed twice respectively with water and ethanol, keeps 7<PH<10, it is centrifugally separating to obtain compound alumine hydroxide colloid C；
6th, colloid C is placed in 85 DEG C of oven for drying, and is placed on 500 DEG C of temperature programmed control roasting 2h in Muffle furnace and is aoxidized
Aluminium D；
7th, aluminium oxide D is ground into powder of the particle diameter less than 200 mesh, adds 50%5A molecular sieves, 1% waterglass conduct
Binding agent, mixes 1-3h in double-spiral conical mixer, obtains uniformly mixed powder E；
8th, uniformly mixed dry powder E is taken out, is put into bowling machine, the balling-up under 20% damp condition, then sealing is put
100 DEG C of baking oven curing 18h are placed in, then is made through 650 DEG C of progress temperature programmed control roastings of Muffle furnace and Woelm Alumina dealcoholysis is made
Agent SE。
Activity rating example：
The Woelm Alumina dealcoholysis agent that above-mentioned instantiation 1~5 in the present invention is prepared carries out dealcoholysis performance test.
Test condition is as follows：
In this experiment, unstripped gas (methanol/N is used in evaluation2) control of import methanol content is empty in 8000-10000ppm or so
400~1500h of speed-1, 35 DEG C of dealcoholysis environment temperature.Obtained dealcoholysis agent is smashed and is sieved, the little particle of 16~40 mesh is obtained, presses
It is fitted into according to certain regular uniform in homemade fixed-bed micro-reactor, it is 5~8 to control catalyst bed ratio of height to diameter.Dealcoholysis agent is commented
Valency flow chart refers to attached drawing 1.Unstripped gas and reactor tail gas detect methanol content with gas-chromatography GC-9560, and detection is limited to
0.02ppm.By to importing and exporting methanol content CInto、CGo out, the real-time air speed Sv of unstripped gas, methanol absorption time t, dealcoholysis agent bed heap
The measure of the parameters such as density d, carrys out the performance of overall merit Woelm Alumina dealcoholysis agent.When just starting to detect in reactor tail gas
When having the methanol of 0.2ppm, acquiescence dealcoholysis agent has inactivated, and capacity at this time is referred to as break through volume, and amount of capacity is by equation below
Calculate：
Wherein, S --- break through volume
mAlcohol--- the quality g of Catalyst Adsorption methanol in experimentation
The quality g of M --- loading catalyst
CInto、CGo out--- experimental provision inlet and outlet methanol content g/m3
Sv --- experimentation gas space velocity h-1
T --- h the time required to experiment penetrates
D --- catalyst bulk density g/ml
Example evaluation result：
Under the test conditions above, Woelm Alumina dealcoholysis agent S example 1-5 being preparedA-EIn Fig. 1 evaluation rubrics
Under its dealcoholysis performance is evaluated, while the radial direction crush strength according to HG/T2782-2011 to obtained dealcoholysis agent
Tested, the results are shown in Table 1：
1 example 1-5 Woelm Alumina dealcoholysis agent S of tableA-EEvaluation result
Prepared it can be seen from 1 test result of table using the preparation method of the Woelm Alumina dealcoholysis agent in the present invention
Dealcoholysis agent highest penetration capacity can reach 16.61%, diameter 1-3mm radial direction crush strength more than 119N/.
Truly to reflect the internal pore structure situation of dealcoholysis agent, using JW-BK112 types N2 adsorption than surface and pore analysis
Instrument tests the pore structure of obtained dealcoholysis agent, and test result is as shown in table 2：
2 example of table, 1~5 Woelm Alumina dealcoholysis agent SA-EPore structure analysis result
Prepared it can be seen from 2 test result of table using the preparation method of the Woelm Alumina dealcoholysis agent in the present invention
Dealcoholysis agent is than surface in 355m2/ more than g, pore volume is in 0.53cm3/ more than g, average pore size between 4~6nm, 95% with
On be all it is mesoporous, contain minimal amount of micropore and macropore.Meanwhile with reference to 2 dealcoholysis agent S of attached drawingAIsothermal inhale (de-) attached curve
With the dealcoholysis agent S of attached drawing 3APore size distribution curve, can from which further follow that, prepared Woelm Alumina dealcoholysis agent belongs to cylinder
Shape type meso-hole structure, pore-size distribution is narrow, and mean pore size is methanol molecules diameterMore than 20 times, can meet alcohols
Molecule frees in and out in dealcoholysis agent duct, and reactivity is higher.
The above specific implementation case, is to carried out in detail to the purpose of the present invention, technical solution and beneficial effect
Describe in detail bright, and be not restricted to the present invention, every any modification within the spirit and principles in the present invention, made, equally replace
Change, improve etc. and belonging within protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of Woelm Alumina dealcoholysis agent, it is characterised in that:The method comprises the following steps that：(1) Al is selected3+As the source of main carrier component, polyethylene glycol is added as expanding agent, mixed solution is configured to, to have Machine amine using direct precipitation method, obtains aluminium glue body as precipitating reagent under conditions of heating water bath mechanical agitation, and colloid is old Change to stable state, obtain colloid A；(2) 5~15% alkaline metal salts are added into colloid A obtained by step (1) to fill as coagent, heating water bath, stirring Divide reaction, control 7<PH<10, mixed sediment B is obtained, obtains aluminium glue body, through centrifuge washing, in the case where temperature is 80~120 DEG C Drying, through the roasting of 400~700 DEG C of Muffle furnace, after be ground into the powder that particle diameter is less than 200 mesh, obtain active oxidation aluminium powder；(3) active oxidation aluminium powder made from step (2) is added into molecular sieve, binding agent, expanding agent, in double-spiral conical mixer It is interior to be uniformly mixed, the spherical of 1~3mm of diameter is prepared under 20~30% damp condition, rear sealing, moisturizing cures in baking oven Fired to stabilization, then through Muffle furnace up to Woelm Alumina dealcoholysis agent.
- 2. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:In step (1), the Al3 +The component of main carrier is one or more of mixtures in aluminium chloride, aluminum nitrate, aluminum sulfate, aluminium salt mass concentration for 5~ 30%；For the molecular weight polyethylene glycol between 300-700, addition accounts for the 1-10% of main carrier quality.
- 3. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:It is described in step (1) Organic amine is any one in the organic amines such as hydramine (MEA, DEA, TEA, DIPA, MDEA), enamine (DETA, TETA, TEPA) Or several mixtures, preferably DEA, MEA, TEA, DETA, TETA, its concentration are 5~30wt%；The quality of aluminium salt and organic amine Than for 1:(1.3~3.5).
- 4. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:It is described in step (1) Water bath heating temperature is 20~100 DEG C, is preferably 60~80 DEG C, and mixing speed is 300~700r/min, the reaction time 0.5 ~3h；The Aging Temperature of the composite colloid A is consistent with reaction temperature, and digestion time is 24~48h.
- 5. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:In step (2), the alkali Metallic salt is in the carbonate or bicarbonate of lithium (Li), sodium (Na), potassium (K), one or more of elements in rubidium (Rb) One or more of mixtures.
- 6. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:In step (2), it is described from Heart wash conditions is wash twice, and alcohol is washed twice.
- 7. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:In step (2), described point Son sieve is one or more of mixtures in A types, X-type, Y type molecular sieve, additive amount 10-50%.
- 8. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:It is described viscous in step (2) Knot agent is calcium oxide, one or more of mixtures in bentonite, kaolin, waterglass, additive amount 1-10%.
- 9. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:In step (2), the expansion Hole agent is mainly sesbania powder, additive amount 1-10%.
- 10. the preparation method of Woelm Alumina dealcoholysis agent as claimed in claim 1, it is characterised in that:It is described in step (3) Cooking conditions heat 12-24h, the roasting condition, with the speed of 10 DEG C/min, temperature 400~700 for 50-150 DEG C for baking oven DEG C, temperature programmed control fires 4-12h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108926988A (en) * | 2018-07-18 | 2018-12-04 | 武汉纺织大学 | A kind of preparation method of copper-based desulfurizing agent, copper-based desulfurizing agent and preparation system |
| CN112427007A (en) * | 2020-11-18 | 2021-03-02 | 山东物华新材料科技有限公司 | Preparation method of activated alumina ball adsorbent |
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| CN105948089A (en) * | 2016-05-03 | 2016-09-21 | 许杰 | High-temperature-resistant and large-specific-surface-area aluminum oxide and preparation method thereof |
| CN106621797A (en) * | 2016-12-09 | 2017-05-10 | 武汉纺织大学 | Efficient composite oxide desulfurizing agent preparation method |
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| WO1991004943A2 (en) * | 1989-09-29 | 1991-04-18 | Exxon Research And Engineering Company | Zeolite aggregates and catalysts |
| CN103100434A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier material containing molecular sieve and alumina |
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| CN112427007A (en) * | 2020-11-18 | 2021-03-02 | 山东物华新材料科技有限公司 | Preparation method of activated alumina ball adsorbent |
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