CN106669852A - Preparation method of aluminum oxide carrier - Google Patents
Preparation method of aluminum oxide carrier Download PDFInfo
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Abstract
The invention discloses a preparation method of an aluminum oxide carrier. The method comprises the following steps: (1) bottom water is added into a pressure zone and a reaction zone of a reactor, ionic liquid I is added, and gelling temperature is adjusted; (2) an aqueous solution of alkaline aluminate is added into the reactor, at the same time CO2 enters the reaction zone from the lower part of the reaction zone, CO2 and the aqueous solution of alkaline aluminate are neutralized for carrying out a sol forming reaction, when water in the pressure zone enters the reaction zone through a semi-permeable membrane, the sol concentration is kept in a concentration range, and the reaction is continuously carried out; (3) after the reaction ends, ultrasonic vibration at the bottom is started, and after aging, washing and drying are carried out, pseudo-boehmite is obtained. (4) mixing and kneading, moulding, drying and calcination of the pseudo-boehmite prepared in the step (3), an adhesive and ionic liquid II are carried out, and the aluminum oxide carrier is obtained. The aluminum oxide carrier has the advantages of high specific surface area, large aperture and pore volume, high lateral compressive strength, and low abrasion; and the product is adapted to be the carrier of boiling bed wax oil, residual oil hydrogenation catalysts.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, specifically a kind of aperture pore volume is larger, and the preparation method of the alumina support with dual pore distribution.
Background technology
It is domestic at present mainly aluminium hydroxide to be prepared with the process route such as ammoniacal liquor or other alkali reprecipitations Jing after acid dissolving using industrial aluminium hydroxide.This method complex manufacturing, the industrial chemicals for needing corrosion protection equipment and consumption costliness.The domestic cost with other industrial byproduct organo-aluminum compound hydrolysis preparations is then much lower.And boehmite impurity content at present prepared by the country is high, particle diameter distribution is uneven, and degree of crystallinity is low, the shortcomings of pore structure is undesirable.
CN85100161A discloses a kind of carbonating technique（CO2Method）The method of production boehmite, the method is raw material using intermediate product-industrial sodium aluminate solution, uses high concentration CO2Gas does precipitating reagent, the quick carbonating plastic under low-temperature and low-concentration and obtain boehmite, carbonating plastic process can be interrupted and carried out with serialization, and resulting product purity is high, and peptization is good.But prepared boehmite crystal grain is imperfect, and particle diameter distribution disperse, degree of crystallinity is low.
CN102861617A discloses a kind of preparation method of double-hole-structuralumina alumina supporter, including weighing a certain amount of boehmite dry glue powder, it is well mixed with appropriate peptizing agent, extrusion aid, the addition amount of ammonium bicarbonate aqueous solution in material is stated then up, by resulting material kneading into plastic, extruded moulding, molding materials are positioned in sealing container roasting after hydrothermal treatment and alumina support are obtained.Described hydro-thermal process temperature is 70 DEG C -120 DEG C, and process time is 5-10 hours.Described roasting is in 600 DEG C of -750 DEG C of roasting 2-4 hours.The mass concentration of described ammonium bicarbonate soln is 40%-80%, and ammonium bicarbonate soln addition is with NH4+And Al3+Calculate, NH4+And Al3+Mol ratio be 0.5-1：1.The inventive method preparation process is simple, and obtained alumina support has dual pore size distribution, preferable mechanical strength, it is adaptable to prepare the fields such as weight, residuum hydrogenating and metal-eliminating catalyst.
Prepared by the way of neutralization plastic more than boehmite at present, the concentration of boehmite colloidal sol is continuously increased in preparation process, colloidal sol rapid aggregation is easily caused into gel, so as to cause the generation of amorphous boehmite, and its particle diameter distribution is uneven, degree of crystallinity is low, the shortcomings of impurity content is high.
Pellicle is a kind of film passed in and out to certain molecule or ion diffusion, to different particles by selective film.Pellicle is used to permeate colloidal sol and measure osmotic pressure etc..Being can be through semipermeable membrane through pellicle made by special process, solvent and electrolyte in solution etc. with macromolecular material, and the larger material of colloid, particulate and molecular weight is then trapped.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation method of alumina support, the inventive method adopts semi-transparent membrane reactor, simultaneously by adding two kinds of ionic liquids in aluminum oxide plastic and kneading process, prepared alumina support, specific surface area is high, aperture pore volume is larger, side pressure strength is high, and abrasion are low, are well suited as the carrier of ebullated bed wax oil, residual oil hydrocatalyst.
The preparation method of the alumina support of the present invention, including following content：
（1）
By M1Respectively and M2、M3Make ionic liquid I, II；
（2）The pressure area of reactor and reaction zone are added into bottom water, and ionic liquid I is added in bottom water in reaction zone, adjust gelling temperature；
（3）The basic aluminate aqueous solution is added in reactor by reactor reaction zone top, while CO2Reaction zone is entered from reaction zone bottom through pellicle, plastic reaction is neutralized with the basic aluminate aqueous solution, aluminum hydroxide sol concentration to be generated is reached after 5～15g/100ml, water in pressure area is entered into by reaction zone by pellicle by compression pump, collosol concentration is maintained in the concentration range, continues to react a period of time；
（4）After reaction terminates, start bottom sonic oscillation, adjust and reactor pH value and be rapidly heated to aging temperature, carry out aging, washing and be dried, obtain boehmite；
（5）By step（4）Prepared boehmite, adhesive and ionic liquid II, carry out kneading, shaping, and then material drying, roasting, obtain alumina support.
In the inventive method, step（1）The M1For one or more in ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate etc., preferably ammonium hexafluorophosphate and/or tetrafluoro boric acid is pressed.
In the inventive method, step（1）Described M2It is one or more in the alkyl ammonium halide of 4 ~ 8 for carbon number, alkyl is preferably one or more in methyl, ethyl, propyl group, more preferably halogenation triethyl ammonium, halogenation tetraethyl ammonium, ethyl ammonium halide, the preferred chlorine of halogen.
In the inventive method, step（1）Described M3It is one or more in the alkyl ammonium halide of 8 ~ 12 for carbon number, it is preferred that one or more in halogenated methyl tri-n-butylamine, halogenation dimethyl di-n-butylamine, halogenation propyl group tri-n-butylamine, halogenation dipropyl di-n-butylamine, halogenated methyl puratized agricultural spray, halogenation dimethyl puratized agricultural spray, halogenation trimethyl puratized agricultural spray etc., preferably halogenated methyl puratized agricultural spray, halogenation dimethyl di-n-butylamine, in one or more, the preferred chlorine of halogen.
In the inventive method, step（1）The preparation method of intermediate ion liquid I can be carried out generally by M using conventional method1And M2It is added to the water, reaction temperature is heated under agitation, isothermal reaction after reaction terminates, is cooled down, and centrifugation obtains ionic liquid I；Wherein M1With M2Mol ratio be 1：1～1：2, reaction condition is generally reaction temperature for 60～150 DEG C, preferably 70～100 DEG C, and the isothermal reaction time is 1～4h, preferably 1～2h.The preparation method and preparation condition of ionic liquid II is identical with ionic liquid I, by the M in said method2It is substituted for M3, that is, obtain ionic liquid II.
In the inventive method, step（1）The addition of intermediate ion liquid I accounts for the 1.2%～3.0% of carrying alumina body weight in terms of auxiliary element quality.
In the inventive method, step（1）Described in plastic reaction temperature be 20～50 DEG C, preferably 25～45 DEG C.
In the inventive method, step（2）Described in alkaline solution be the alkali metal aluminate aqueous solution or the alkaline precipitating agent aqueous solution；The alkali metal aluminate aqueous solution is NaAlO2Or KAlO2The aqueous solution, concentration is with Al2O3It is calculated as 8～35g/100mL；The flow of described alkaline solution is 5～30ml/min, preferably 15～25ml/min.Step（2）Middle CO2Purity be 30%～100%, preferably 80% ~ 100%, flow be 2.0～5.0L/min, preferably 2.5～4.5L/min.
In the inventive method, step（2）The volume of described bottom water accounts for the 1/10～1/5 of reactor volume；
In the inventive method, step（3）Described in aluminum hydroxide sol concentration reach 5～15g/100mL time be 10～60min, preferably 15～40min.
In the inventive method, step（3）Described in pressure area and reaction zone pressure reduction（△P）Between 0.5～5.0, preferably 1.0～4.0MPa.The pressure reduction during plastic with reaction zone in increasing for solution and be continuously increased, its purpose is to keep reaction zone in collosol concentration change within the specific limits.
In the inventive method, step（3）The described continuation reaction time is 30～120 minutes, preferably 35～90 minutes.
In the inventive method, step（3）Described pellicle is one or more in biomembrane, physical film or composite membrane, such as：The pericystium of animal, casing, egg shell membrane, one or more in also artificial pellicle such as glassine paper, the collodion membrane for preparing.The aperture of the pellicle<1nm.The maximum pressure that the pellicle can bear is 100～200GPa.
In the inventive method, step（4）The frequency of described sonic oscillation is 2000～5000Hz, preferably 2500～4500Hz.
In the inventive method, step（4）Described pH value range is 5.0～8.0, preferably 5.5～7.0；Described programming rate is 5～20 DEG C/min, preferably 10～15 DEG C/min；Described aging temperature is 60～100 DEG C, preferably 70～90 DEG C；The aging time is 0.5～3.0h, preferably 1.0～2.0h；
In the inventive method, step（4）Described washing process is：Water is entered into pressor areas by the pellicle of reaction zone bottom to the reaction zone pressurization of reactor, material is washed, treat material washing after the completion of add into pressure area again certain water purification then proceed to pressurization water purification is pressed into reaction zone, material is washed next time, then pressurize to reaction zone again and water is entered into pressor areas by the pellicle of reaction zone bottom, after so cleaning material repeatedly for several times, pure material is obtained；General described washing times are 2～3 times.
In the inventive method, step（4）Degree of crystallinity >=85% of prepared boehmite, preferably >=90%.Boehmite particle diameter distribution has following property：＜ 50nm particle diameters proportion is 10%～20%；It is 5%～10% that 50～90nm particle diameters proportion is 70%～80%, ＞ 90nm particle diameters proportion.Degree of crystallinity in the inventive method is measured using XRD, and particle diameter distribution is measured using laser particle analyzer.
In the inventive method, step（5）The addition of intermediate ion liquid II accounts for the 0.8%～2.0% of carrying alumina body weight in terms of auxiliary element quality.
In the inventive method, step（5）Described baking temperature is 100～150 DEG C, and drying time is 2.5～3.5h；Sintering temperature is 500～900 DEG C, and roasting time is 3～6h.
Alumina support prepared by the inventive method, with following property：300 ~ 320m of specific surface area2/ g, 0.9 ~ 1.2ml/g of pore volume, with dual pore distribution, aperture is 10 ~ 15nm and 15 ~ 30nm；The wherein pore size distribution of 10 ~ 15nm accounts for total pore volume 35% ~ 40%, and the pore size distribution of 15-30nm accounts for the 30% ~ 35% of total pore volume；On the basis of carrying alumina body weight, auxiliary agent accounts for 2% ~ 5% with element gauge, and wherein auxiliary agent is the one kind in several combinations of following I, II and III：I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron, preferred III- fluorine, phosphorus and boron.In alumina support of the present invention, in terms of auxiliary element, when auxiliary agent is I, fluorine accounts for the 50%～55% of auxiliary agent quality, and phosphorus accounts for the 45%～50% of auxiliary agent gross mass；When auxiliary agent is II, fluorine accounts for the 50%～55% of auxiliary agent quality, and boron accounts for the 45%～50% of auxiliary agent gross mass；When auxiliary agent is III, fluorine accounts for the 50%～55% of auxiliary agent total amount, and phosphorus accounts for the 30% ~ 35% of auxiliary agent total amount, and boron accounts for the 15%～20% of auxiliary agent total amount.The intensity of described alumina support >=150N/ grains, abrasion≤0.05wt%.
Present invention simultaneously provides a kind of semi-transparent membrane reactor, pressure area I, reaction zone and pressure area II are followed successively by from left to right, are separated by by pellicle between pressure area and reaction zone, the connection of reaction zone top charging aperture I and II, I and II are connected respectively with compression pump for pressure area, and pressure area top is enclosed construction.
Compared with prior art, the inventive method has advantages below：
1st, this method adds ionic liquid I and II to adjust the pore structure and acid distribution of alumina support in the process of plastic and kneading so that there is carrier dual pore distribution, i.e. pore size distribution to be concentrated mainly on 10 ~ 15nm and 15 ~ 30nm；The introducing that the auxiliary agents such as auxiliary agent fluorine, boron, phosphorus pass through small molecular ion liquid I, modifies 10 ~ 15nm ducts；The introducing that the auxiliary agents such as auxiliary agent fluorine, boron, phosphorus pass through macromolecular ionic liquid II, modifies 15 ~ 30nm ducts, so makes it cooperate, and so as to improve the combination property of alumina support, and then improves desulfurization and the denitrification activity of catalyst.
2nd, during alumina support plastic, hydrone and electrolyte is only allowed to pass through using pellicle using semi-transparent membrane reactor, and the principle that colloidal sol cannot be passed through, stable colloidal sol is formed in initial reaction stage solution in preparation process, after aluminum oxide reaches finite concentration in colloidal sol, by two ends pressure reduction by water penetration to reactor, collosol concentration is constant in so as to keep reactor, under the conditions of low temperature and constant density, colloidal sol keeps stable and continues to increase, and the aggregation rate of colloidal sol is reduced, formation contributes in a large number the boehmite nucleus for crystallizing；Secondly by the pyroreaction stage（Aging reaction）, increase the Brownian movement of colloidal sol itself, so that the homogeneous colloidal sol of system occurs gel, the boehmite for ultimately forming has higher degree of crystallinity and size of microcrystal is homogeneous；Meanwhile, the foreign ion in colloidal sol by semipermeable membrane to both sides water quite in, the content of impurity in the boehmite for ultimately forming is reduced, so as to improve the purity of boehmite；
4th, the alumina support prepared by this method, specific surface area is high, and aperture pore volume is larger, and side pressure strength is high, and abrasion are low, are well suited for for the preparation of ebullated bed wax oil, Residual catalyst and carrier.
Description of the drawings
Fig. 1 is the schematic diagram of semi-transparent membrane reactor in the present invention.
Wherein 1- reaction zones；2- pressure areas；3- charging apertures；4- pellicles.
Specific embodiment
The preparation method of the alumina support of the present invention, comprises the following steps：
（a）What the concentration and compound method of working solution was well known to the skilled person.Such as, the concentration of the acid aluminium salt aqueous solution is with Al2O3It is calculated as 3g/100mL～15g/100mL；The concentration of composite alkali aluminum saline solution is with Al2O38g/100mL～35g/100mL is calculated as, described composite alkali aluminum saline solution is selected from NaAlO2、KAlO2One or more in the aqueous solution, preferred NaAlO2The aqueous solution；
（b）By M1Respectively and M2、M3Make ionic liquid I, II；
（c）Bottom water and a certain amount of ionic liquid I are added to the bottom of reactor 1, and be heated to 25～45 DEG C；
（d）Adjust the charging rate of charge pipe on reactor, by finite concentration basic metal salt solutions are with 15～20ml/min flows and flow into the middle of reactor, simultaneously 2.0～5.0L/min of pellicle is passed through from bottom, preferably 2.5～4.5L/min is passed through the CO that purity is 30% ~ 100%2Gas, 15～30min of plastic aluminum hydroxide sols to be generated are reached after 5～15g/100ml, and specific pressure is applied in pressure at both sides case, keep pressure reduction to change between 0.5～4.0MPa, collosol concentration in solution is maintained in the concentration range, to continue to react 0.5 ~ 1.5h；
（e）After reaction terminates, start bottom sonic oscillation, adjust certain rotating speed, adjust reactor pH value 5.0～7.0 and raised reaction temperature with 10～20 DEG C/min speed, carry out aging 1.0～2.0h, ageing process pH is 5.0～6.0.After aging end, water is entered into pressor areas by pellicle by reaction zone to the top compression of reactor.Add into pressure area certain water purification after dry materials to then proceed to after pressurization cleans material for several times repeatedly, that is, obtain required nano pseudo boehmite.
（f）By above-mentioned prepared boehmite, adhesive and a certain amount of ionic liquid II, being mediated with kneading machine becomes after plastic, sends into comminutor and granulates, and the use of screen cloth is 40 mesh.Start comminutor, adjust rotary speed in 1500～2500 turns/min, 1.0～5.0min of granulation time, granulation will obtain required alumina support after terminating after material drying, the roasting of balling-up.
The semi-transparent membrane reactor of the present invention, pressure area I, reaction zone and pressure area II are followed successively by from left to right, are separated by by pellicle between pressure area and reaction zone, reaction zone top connection charging aperture, I and II are connected respectively with compression pump for pressure area, and pressure area top is enclosed construction.
The preparation method of the alumina support of the present invention is described in more detail below by specific embodiment.Embodiment does not constitute the restriction of the scope of the present invention simply to the illustration of the specific embodiment of the inventive method, and the feed postition of auxiliary agent is one or more in various incorporation ways.
In the embodiment of the present invention and comparative example：Nitric acid（Concentration is 65wt%）, citric acid（Concentration is 99wt%）Pure to analyze, sesbania powder is pure for chemistry, the production of Shenyang Li Cheng chemical reagent works；NaOH, aluminium hydroxide, aluminum sulfate, Yantai Heng Hui Chemical Co., Ltd.s；Ammonium tetrafluoroborate, sodium hexafluoro phosphate, Wuhan sea Dehua work Development Co., Ltd；Triethyl ammonium chloride, dimethyl benzene ammonium chloride, trimethylphenyl ammonium chloride, aminomethyl phenyl ammonium chloride, etamon chloride, Qingdao Golden Horse Chemical Co., Ltd.；CO2（85% purity）, sodium metaaluminate be purchased from Yantai Heng Hui Chemical Co., Ltd.s.
Degree of crystallinity is measured using XRD in the inventive method；Particle diameter distribution is measured using laser particle analyzer；SO4 2+, Na+It is measured using HPLC-ION；Intensity is measured using side pressure strength instrument；Abrasion are measured using abrasion instrument, and minute is 1h.
Embodiment 1
Triethyl ammonium chloride 400g, sodium hexafluoro phosphate 220g, pure water 450g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 450g of ionic liquid I, aqueous about 3.5wt%, yield 72wt%.
Trimethylphenyl ammonium chloride 500g, sodium hexafluoro phosphate 260g, pure water 450g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 550g of ionic liquid II, aqueous about 3.5wt%, yield 74wt%.
1L bottom water and 40g ionic liquids I are added to the bottom of reactor 1, and reaction temperature is adjusted into 30 DEG C.The charging rate of charge pipe on reactor is adjusted, by the NaAlO that concentration is 10g/100ml2Solution 20ml/min flows and by bottom by pellicle with 2.5L/min flows inject CO2Plastic 20min aluminum hydroxide sol to be generated is reached after 7.6g/100ml, apply specific pressure in pressure at both sides area, keep pressure reduction △ P between 0.5～2.0MPa, maintenance collosol concentration is between 5～15g/100ml, continue to react 1.0h, after reaction terminates, start sonic oscillation, adjust reactor pH value 5.0 and reaction temperature is increased to by 80 DEG C of high temperature section with 10 DEG C/min speed, aging 1.0h is carried out, aging pH value is 5.0.After aging end, water is entered into pressor areas by pellicle by reaction zone to the top compression of reactor.Certain water purification being added after dry materials into pressure area and then proceeding to the nano pseudo boehmite cleaned repeatedly needed for material is obtained afterwards, that is, for 2 times that pressurizes, numbering is GJ-1, and property is shown in Table 1.
The above-mentioned boehmites of 1000g are weighed, 14g nitric acid, 568g water purification and 20g ionic liquids II are become after plastic with kneading machine kneading, be sent in comminutor and granulate, and the use of screen cloth are 40 mesh.After starting comminutor, regulation rotary speed is 1500 turns/min, and granulation time is 1.5min.Balling-up material is dried into 3h at 100 DEG C, at 600 DEG C after roasting 3h, required aluminum oxide micro-sphere is obtained, numbering is WQ-1, and property is shown in Table 2.
Embodiment 2
Triethyl ammonium chloride 300g, sodium hexafluoro phosphate 160g, pure water 350g, mixing is heated under agitation 100 DEG C, after constant temperature 2.5h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 420g of ionic liquid I, aqueous about 3.7wt%, yield 72wt%.
Dimethyl benzene ammonium chloride 600g, sodium tetrafluoroborate 300g, pure water 550g, mixing is heated under agitation 70 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 550g of ionic liquid II, aqueous about 4.0wt%, yield 74wt%.
2L bottom water and 35g ionic liquids I are added to the bottom of reactor 1, and reaction temperature is adjusted into 40 DEG C.The charging rate of charge pipe on reactor is adjusted, by the NaAlO that concentration is 15g/100ml2Solution 25ml/min flows and by bottom by pellicle with 3.5L/min flows inject CO2Plastic 30min aluminum hydroxide sol to be generated is reached after 10g/100ml, apply specific pressure in pressure at both sides area, keep pressure reduction △ P between 0.5～4.0MPa, maintenance collosol concentration is between 5～15g/100ml, continue to react 0.5h, after reaction terminates, start sonic oscillation, adjust reactor pH value 5.5 and reaction temperature is increased to by 90 DEG C of high temperature section with 20 DEG C/min speed, aging 1.5h is carried out, aging pH value is 6.0.After aging end, water is entered into pressor areas by pellicle by reaction zone to the top compression of reactor.Certain water purification being added after dry materials into pressure area and then proceeding to the nano pseudo boehmite cleaned repeatedly needed for material is obtained afterwards, that is, for 3 times that pressurizes, numbering is GJ-2, and property is shown in Table 1.
The above-mentioned boehmites of 2000g are weighed, 30g nitric acid, 120g water purification and 23g ionic liquids II are become after plastic with kneading machine kneading, be sent in comminutor and granulate, and the use of screen cloth are 40 mesh.After starting comminutor, regulation rotary speed is 2000 turns/min, and granulation time is 2.0min.Balling-up material is dried into 4h at 120 DEG C, at 650 DEG C after roasting 4h, required aluminum oxide micro-sphere is obtained, numbering is WQ-2, and property is shown in Table 2.
Embodiment 3
Etamon chloride 450g, sodium tetrafluoroborate 250g, pure water 500g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 650g of ionic liquid I, aqueous about 3.9wt%, yield 75wt%.
Aminomethyl phenyl ammonium chloride 500g, sodium hexafluoro phosphate 260g, pure water 450g, mixing is heated under agitation 90 DEG C, after constant temperature 3h, and clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains the 550g of ionic liquid II, aqueous about 3.5wt%, yield 74wt%.
1.5L bottom water and 30 ionic liquids I are added to the bottom of reactor 1, and reaction temperature is adjusted into 25 DEG C.Charging rate on reactor is adjusted, by the NH that concentration is 10g/100ml4OH solution ml/min flows and by bottom by pellicle with 4.5L/min flows inject CO2, aluminum hydroxide sol to be generated is reached after 7.4g/100ml after plastic 20min, apply specific pressure in pressure at both sides area, pressure reduction △ P are kept between 0.7～2.0MPa, collosol concentration is maintained between 5～15g/100ml, continues to react 1.0h, after reaction terminates, start paddle, regulation rotating speed is 1500r/min, adjusts reactor pH value 6.0 and reaction temperature is increased into 75 DEG C of high temperature section with 15 DEG C/min speed, aging 2.0h is carried out, aging pH value is 5.0.After aging end, water is entered into pressor areas by pellicle by reaction zone to the top compression of reactor.Certain water purification being added after dry materials into pressure area and then proceeding to the nano pseudo boehmite stone cleaned repeatedly needed for material is obtained afterwards, that is, for 2 times that pressurizes, numbering is GJ-3, and property is shown in Table 1.
The above-mentioned boehmites of 1500g are weighed, 20g nitric acid, 105g water purification and 16g ionic liquids II are become after plastic with kneading machine kneading, be sent in comminutor and granulate, and the use of screen cloth are 40 mesh.After starting comminutor, regulation rotary speed is 2500 turns/min, and granulation time is 3.0min.Balling-up material is dried into 2h at 150 DEG C, at 580 DEG C after roasting 5h, required aluminum oxide micro-sphere is obtained, numbering is WQ-3, and property is shown in Table 2.
Comparative example 1
By the 6L sodium metaaluminate aqueous solution（Al2O3Concentration is 20g/100mL）With 9L aluminum sulfate aqueous solutions（Al2O3Concentration is 5g/100mL）It is respectively charged into the container with pump, is connected respectively on the charging aperture I and charging aperture II of the reactor equipped with 2L distilled water and 40g ionic liquids I, 65 DEG C will be heated in reactor；Start the propeller in reactor, adjustment rotating speed is 1000r/min, after a period of stabilisation, the flow velocity of charging aperture I and charging aperture II is adjusted to 20ml/min, starts to inject sodium metaaluminate and aluminum sulfate aqueous solution, adjust pH value to 7.0, after neutralization a period of time, after aging 1.5h, mother liquor is separated by filtration, is washed, it is dried, prepared boehmite, numbering is GF-4, and property is shown in Table 1.
The above-mentioned boehmites of 2000g are weighed, 30g nitric acid, 120g water purification and ionic liquid I are become after plastic with kneading machine kneading, be sent in comminutor and granulate, and the use of screen cloth are 40 mesh.After starting comminutor, regulation rotary speed is 2000 turns/min, and granulation time is 2.0min.Balling-up material is dried into 4h at 120 DEG C, at 650 DEG C after roasting 4h, required aluminum oxide micro-sphere is obtained, numbering is WQ-4, and property is shown in Table 2.
Comparative example 2
By the 6L sodium metaaluminate aqueous solution（Al2O3Concentration is 20g/100mL）Load in the container with pump, be connected on the charging aperture of the reactor equipped with 2L distilled water, 65 DEG C will be heated in reactor；Start the propeller in reactor, adjustment rotating speed is 1000r/min, after a period of stabilisation, adjust the flow velocity of charging aperture to 20ml/min, start to inject the sodium metaaluminate aqueous solution, while being passed through CO in solution with 4.5L/min2Gas, adjusts pH value to 6.0, and after neutralization a period of time, after aging 1.5h, aging pH value is 6.0, is separated by filtration mother liquor, is washed, and is dried, and prepared boehmite, numbering is GF-5, and property is shown in Table 1.
The above-mentioned boehmites of 1500g, 25g nitric acid and 100g water purification are weighed, being mediated with kneading machine becomes after plastic, be sent in comminutor and granulate, the use of screen cloth is 40 mesh.After starting comminutor, regulation rotary speed is 3000 turns/min, and granulation time is 2.5min.Balling-up material is dried into 3h at 120 DEG C, at 650 DEG C after roasting 3.5h, required aluminum oxide micro-sphere is obtained, numbering is WQ-5, and property is shown in Table 2.
The property of boehmite prepared by the embodiment of table 1 and comparative example.
Boehmite specific surface area by prepared by the property of table 1 can be seen that using the inventive method is high, and pore volume is big, and degree of crystallinity is high, and even particle size distribution, impurity content is low, is suitable for the preparation of the inferior raw material such as wax oil, heavy oil catalyst carrier for hydrgenating and catalyst.
The property of alumina support prepared by the embodiment of table 2 and comparative example.
Active appraisal experiment：
Catalyst in embodiment 1-3 and comparative example 1-2 is loaded after hydrogenation active metals component using conventional method, respectively numbering is CT-1, CT-2, CT-3, CD-1, CD-2, the activity rating of catalyst is carried out as raw material with the miscella of VGO and DAO, catalyst activity evaluation experimental is carried out on 50mL small hydrogenation devices, and presulfurization is carried out to catalyst before activity rating.Catalyst is in reaction stagnation pressure 8.0MPa, volume space velocity 1.0h during liquid-1, hydrogen to oil volume ratio 800：1, reaction temperature is 380 DEG C, the results are shown in Table 4 and 5.
The property of the embodiment of table 3 and comparative example alumina support prepared catalyst.
The raw material oil nature of table 4.
The catalyst activity evaluation result of table 5.
From table 5, the hydrodenitrogeneration of catalyst prepared by the present invention, hydrodesulfurization and metal removal activity are significantly better than comparative example.
Claims (16)
1. a kind of preparation method of alumina support, it is characterised in that including following content：（1）By M1Respectively and M2、M3Make ionic liquid I, II；（2）The pressure area of reactor and reaction zone are added into bottom water, and ionic liquid I is added in bottom water in reaction zone, adjust gelling temperature；（3）The basic aluminate aqueous solution is added in reactor by reactor reaction zone top, while CO2Reaction zone is entered from reaction zone bottom through pellicle, plastic reaction is neutralized with the basic aluminate aqueous solution, aluminum hydroxide sol concentration to be generated is reached after 5～15g/100ml, water in pressure area is entered into by reaction zone by pellicle by compression pump, collosol concentration is maintained in the concentration range, continues to react a period of time；（4）After reaction terminates, start bottom sonic oscillation, adjust and reactor pH value and be rapidly heated to aging temperature, carry out aging, washing and be dried, obtain boehmite；（5）By step（4）Prepared boehmite, adhesive and ionic liquid II, carry out kneading, shaping, and then material drying, roasting, obtain alumina support；
Step（1）The M1 is one or more in ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate；
Step（1）The M2 is that carbon number is one or more in the alkyl ammonium halide of 4 ~ 8；
Step（1）Described M3 is that carbon number is one or more in the alkyl ammonium halide of 8 ~ 12.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）The addition of intermediate ion liquid I accounts for the 1.2%～3.0% of carrying alumina body weight in terms of auxiliary element quality.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in plastic reaction temperature be 20～50 DEG C.
4. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in alkaline solution be the alkali metal aluminate aqueous solution or the alkaline precipitating agent aqueous solution；The alkali metal aluminate aqueous solution is NaAlO2Or KAlO2The aqueous solution, concentration is with Al2O3It is calculated as 8～35g/100mL；The flow of described alkaline solution is 5～30ml/min.
5. in accordance with the method for claim 1, it is characterised in that：Step（2）Middle CO2Purity be 30%～100%, flow be 2.0～5.0L/min.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）The volume of described bottom water accounts for the 1/10～1/5 of reactor volume.
7. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in aluminum hydroxide sol concentration reach 5～15g/100mL time be 10～60min.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in pressure area and reaction zone pressure reduction be 0.5～5.0 between.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）The described continuation reaction time is 30～120 minutes.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described pellicle is one or more in biomembrane, physical film or composite membrane；The aperture of the pellicle<1nm；The maximum pressure that the pellicle can bear is 100～200GPa.
11. in accordance with the method for claim 1, it is characterised in that：Step（4）The frequency of described sonic oscillation is 2000～5000Hz.
12. in accordance with the method for claim 1, it is characterised in that：Step（4）Described pH value range is 5.0～8.0；Described programming rate is 5～20 DEG C/min.
13. in accordance with the method for claim 1, it is characterised in that：Step（4）Described aging temperature is 60～100 DEG C, and the aging time is 0.5～3.0h.
14. according to the method described in claim 1 ~ 13 any claim, it is characterised in that：Step（4）Degree of crystallinity >=85% of prepared boehmite；Boehmite particle diameter distribution has following property：＜ 50nm particle diameters proportion is 10%～20%；It is 5%～10% that 50～90nm particle diameters proportion is 70%～80%, ＞ 90nm particle diameters proportion.
15. in accordance with the method for claim 1, it is characterised in that：Step（5）The addition of intermediate ion liquid II accounts for the 0.8%～2.0% of carrying alumina body weight in terms of auxiliary element quality.
16. according to method this preparation described in claim 1 ~ 13 any claim alumina support, with following property：300 ~ 320m of specific surface area2/ g, 0.9 ~ 1.2ml/g of pore volume, with dual pore distribution, aperture is 10 ~ 15nm and 15 ~ 30nm；The wherein pore size distribution of 10 ~ 15nm accounts for total pore volume 35% ~ 40%, and the pore size distribution of 15-30nm accounts for the 30% ~ 35% of total pore volume；On the basis of carrying alumina body weight, auxiliary agent accounts for 2% ~ 5% with element gauge, and wherein auxiliary agent is the one kind in several combinations of following I, II and III：I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron；The intensity of described alumina support >=150N/ grains, abrasion≤0.05wt%.
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| CN111003721A (en) * | 2019-12-30 | 2020-04-14 | 池州学院 | Preparation method of high-purity alumina |
| CN115724450A (en) * | 2022-10-21 | 2023-03-03 | 黄山天之都环境科技发展有限公司 | Preparation method of alumina solid catalyst carrier |
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| CN103771467A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of large-particle-size alumina dry glue |
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| CN109320282A (en) * | 2018-11-13 | 2019-02-12 | 江西宏柏新材料股份有限公司 | The method for preparing SiC aeroge by ultrasonic mixing silicon source and carbon source |
| CN111003721A (en) * | 2019-12-30 | 2020-04-14 | 池州学院 | Preparation method of high-purity alumina |
| CN115724450A (en) * | 2022-10-21 | 2023-03-03 | 黄山天之都环境科技发展有限公司 | Preparation method of alumina solid catalyst carrier |
| CN115724450B (en) * | 2022-10-21 | 2024-01-19 | 黄山天之都环境科技发展有限公司 | Preparation method of alumina solid catalyst carrier |
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