CN103566888B - Activation method for p-xylene adsorbent carrier and preparation method of p-xylene adsorbent - Google Patents
Activation method for p-xylene adsorbent carrier and preparation method of p-xylene adsorbent Download PDFInfo
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Abstract
The invention discloses an activation method for a p-xylene adsorbent carrier. The method comprises the following steps: in the presence of air flow, performing microwave drying on formed adsorbent carrier particles with the water content of not lower than 30wt% to reduce the water content in the formed adsorbent carrier particles after drying to below 18wt%, preferably 16-18wt%; in the presence of the air flow, roasting the formed absorbent carrier particles after forming to reduce the water content in the formed adsorbent carrier particles after roasting to below 3.5wt%. The invention further provides a preparation method of a p-xylene adsorbent. According to the activation method for the p-xylene adsorbent carrier, provided by the invention, the defect that the adsorption amount of the adsorbent carrier prepared by a molecular sieve is obviously reduced can be effectively relieved, the defect that the adsorption amount of an adsorbent prepared by the molecular sieve in the prior art is obviously reduced can be further effectively relieved, and the mechanical strength is also stronger.
Description
Technical field
The present invention relates to a kind of activation method of paraxylene adsorbing agent carrier and a kind of preparation method of paraxylene adsorbent.
Background technology
Paraxylene (PX) is important basic chemical industry raw material, industrially normally obtains from containing being separated ethylbenzene, paraxylene, meta-xylene and the mixed C 8 aromatics of ortho-xylene.Because four kinds of C8 aronmatic boiling points are close, adopt conventional rectifying mode to be difficult to be separated, at present, industrial employing isomerization-adsorptive separation technology produces paraxylene, and the core of this technique is adsorbent.
Conventional adsorbent has: the natural materials such as atlapulgite, diatomite; Active carbon; Silica gel; Activated alumina; Synthetic zeolite, also known as molecular sieve; Synthetic resin.Research for paraxylene adsorbent mainly concentrates on adsorbent of molecular sieve.The method preparing adsorbent of molecular sieve mainly comprises prepares carrier, in-situ crystallization and cation exchange, very ripe to the research of in-situ crystallization and cation exchange, but rarely has report for the research of carrier specially.
CN1565718A discloses a kind of paraxylene adsorbent and preparation method, the method comprises: size of microcrystal is that NaX or the NaKX zeolite powder of 0.1-0.4 micron mixes with the mass ratio of kaolin by 88-95:5-12 by (1), and rolling on water spray limit, rolling former top makes it balling-up; (2) bead shaping for above-mentioned rolling is sieved into the bead of 0.60-0.80 millimeter and 0.35-0.60 millimeter, then carries out rolling shaping, dry, roasting by the mass ratio mixing of 20-30:70-80; (3) mixed solution of the bead sodium hydroxide solution after roasting or NaOH and sodium metasilicate is processed at 90-100 DEG C, make kaolin in-situ crystallization wherein be X-type zeolite, then dry, roasting; (4) carry out cation exchange with the soluble salt solutions of barium or the soluble salt solutions of potassium and barium, then wash, activate.Described activation generally with hot-air or nitrogen for medium is to remove moisture unnecessary in adsorbent, described activation temperature is 80-200 DEG C, and the time is 24-72 hour.This activating process is consuming time longer, and activation efficiency is lower.
In addition, in the method preparing adsorbent of molecular sieve, ubiquity a problem, exactly using molecular sieve as after the active component of adsorbent is prepared into adsorbent, the shortcoming that the adsorbance that there is molecular sieve obviously declines.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of activation method of paraxylene adsorbing agent carrier and a kind of paraxylene adsorbent, the method can effectively alleviate molecular sieve become adsorbing agent carrier after the shortcoming that obviously declines of adsorbance, thus the shortcoming that after effectively alleviation becomes adsorbent by molecular sieve, adsorbance obviously declines, the adsorbance of paraxylene adsorbent can be improved thus.
The present inventor finds in an experiment, the adsorbance of carrier in adsorbent process is become to decline obviously at molecular sieve, by improving by the activation method of the adsorbing agent carrier of molecular sieve, alleviate the obvious decline being become adsorbance after adsorbing agent carrier by molecular sieve, and improve the adsorbance of adsorbing agent carrier, thus can effectively alleviate become adsorbent by molecular sieve after the shortcoming that obviously declines of adsorbance.
For above-mentioned purpose, the invention provides a kind of activation method of paraxylene adsorbing agent carrier, wherein, under the method is included in the existence of air stream, water content is not less than 30 % by weight shaping after adsorbing agent carrier particle carry out microwave drying, make dry after described shaping after the water content of adsorbing agent carrier particle be reduced to less than 18 % by weight, preferred 16-18 % by weight; And under the existence of air stream, by dried described shaping after adsorbing agent carrier particle carry out roasting, the water content of the adsorbing agent carrier particle after to make after roasting described shaping is reduced to less than 3.5 % by weight.
Present invention also offers a kind of preparation method of paraxylene adsorbent, the method comprises the paraxylene adsorbing agent carrier through overactivation is prepared into paraxylene adsorbent, and wherein, the method for activation paraxylene adsorbing agent carrier is method as above.
The present inventor is found by a large amount of experiments, under the existence of air stream, by microwave drying and roasting, and the shortcoming that the adsorbance effectively can alleviating obtained adsorbing agent carrier particle obviously declines.Infer that this can may make adsorbing agent carrier particles by heat even due to microwave drying, and in the process of dry and roasting, be the existence of free air-flow, water vapour can be taken away as early as possible, reduce the time of water vapour and adsorbing agent carrier particle contacts, special in roasting process, the existence that can reduce high temperature air stream and steam as much as possible causes molecular sieve to stand the impact of high-temperature water heat ageing, thus alleviate molecular sieve make adsorbing agent carrier after the defect that obviously declines of adsorbance.
Under preferable case of the present invention, by controlling air stream when microwave drying and roasting, during as microwave drying, the frost point of described air stream is greater than-50 DEG C and dew point is less than 50 DEG C, is preferably frost point and is greater than-10 DEG C and dew point is less than 20 DEG C; During roasting, the frost point of air stream, for being more than or equal to-80 DEG C, is preferably-20 DEG C to-30 DEG C.Air stream when controlling microwave drying and roasting in above-mentioned scope, can alleviate further molecular sieve make adsorbing agent carrier after the defect that obviously declines of adsorbance.
Activation method provided by the invention is by achieving the effective activation to adsorbing agent carrier to the drying of adsorbing agent carrier after shaping, the improvement of roasting technique, effectively alleviate the shortcoming that after becoming adsorbing agent carrier by molecular sieve in prior art, adsorbance obviously declines, also the shortcoming that after becoming adsorbent by molecular sieve in prior art, adsorbance obviously declines is alleviated, compared with prior art improve the adsorbance of adsorbent, and the adsorbent obtained can be made to take into account stronger mechanical strength.In addition, the method for microwave drying that the present invention adopts, not only increases production efficiency, and economic environmental protection, and method simply, easily operates.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the present invention, under the activation method of described paraxylene adsorbing agent carrier is included in the existence of air stream, water content is not less than 30 % by weight shaping after adsorbing agent carrier particle carry out microwave drying, make dry after described shaping after the water content of adsorbing agent carrier particle be reduced to less than 18 % by weight, preferred 16-18 % by weight; And under the existence of air stream, by dried described shaping after adsorbing agent carrier particle carry out roasting, the water content of the adsorbing agent carrier particle after to make after roasting described shaping is reduced to less than 3.5 % by weight.
In the present invention, when after microwave drying, described shaping after the water content of adsorbing agent carrier particle when can cause roasting below higher than 18 % by weight molecular sieve adsorbance decline too fast; And when the water content of the adsorbing agent carrier particle after described shaping after roasting can cause higher than 3.5 % by weight the absorption property reducing adsorbent; Therefore, when controlling the water content after microwave drying and the water content after roasting in above-mentioned scope, can effectively alleviate molecular sieve make adsorbent after the defect that obviously declines of adsorbance.
Goal of the invention of the present invention can be realized according to preceding method of the present invention, in order to better realize goal of the invention of the present invention, for the present invention, under preferable case, the air stream used during microwave drying, can carry out drying process according to prior art, make the frost point of dried air stream be greater than-50 DEG C and dew point is less than 50 DEG C, more preferably the frost point of described air stream is greater than-10 DEG C and dew point is less than 20 DEG C, realizes effect of the present invention better.When carrying out microwave drying, can according to described shaping after the flow of quality choice air stream of adsorbing agent carrier particle, and described shaping after the quality of adsorbing agent carrier particle and the flow of air stream can select in relative broad range, as long as make dry after described shaping after the water content of adsorbing agent carrier particle be reduced to less than 18 % by weight, usually can be reduced to 16-18 % by weight.Under preferable case, relative to the adsorbing agent carrier particle after shaping described in 500Kg, the flow of air stream is 100-1000Nm
3/ h, is more preferably 300-400Nm
3/ h.
According to activation method of the present invention, the present invention does not specially require the equipment carrying out microwave drying, the time of microwave drying is not also specially required, as long as make dry after described shaping after the water content of adsorbing agent carrier particle be reduced to less than 18 % by weight, usually can be reduced to 16-18 % by weight.Under preferable case, the power of the equipment of described microwave drying is 100-500KW, is more preferably 250-400KW; The time of microwave drying is 30-300min, is more preferably 50-70min.
According to activation method of the present invention, in order to better realize goal of the invention of the present invention, for the present invention, under preferable case, the air stream used during roasting, can carrying out drying process according to prior art, making the frost point of dried air stream for being more than or equal to-80 DEG C, be more preferably-20 DEG C to-30 DEG C, realize effect of the present invention better.When carrying out roasting, can according to dried described shaping after the flow of quality choice air stream of adsorbing agent carrier particle, and dried described shaping after the quality of adsorbing agent carrier particle and the flow of air stream can select in relative broad range, as long as after making roasting described shaping after the water content of adsorbing agent carrier particle be reduced to less than 3.5 % by weight.Under preferable case, relative to the adsorbing agent carrier particle after shaping described in 500Kg, the flow of air stream is 200-3000Nm
3/ h, is preferably 1600-2000Nm
3/ h.
According to activation method of the present invention, wherein, the selectable range of the temperature and time of roasting is wider, if after roasting can be made described shaping after the water content of adsorbing agent carrier particle be reduced to less than 3.5 % by weight.Under preferable case, the temperature of roasting is 500-650 DEG C, is more preferably 530-560 DEG C; The time of roasting is 1-5h, is more preferably 2-3h.
In the present invention, described roasting apparatus can be roasting apparatus well known in the art, is generally the equipment of interior vent flow, is preferably vertical heater.
According to activation method of the present invention, under normal circumstances, before drying, described shaping after the water content of adsorbing agent carrier particle be not less than 30 % by weight, such as, conventionally carry out shaping after, described shaping after the water content of adsorbing agent carrier particle be 30-50 % by weight.
According to the present invention, described shaping after the preparation method of adsorbing agent carrier particle can carry out with reference to prior art, such as generally, described shaping after the preparation method of adsorbing agent carrier particle comprise molecular sieve and binding agent mixing, and described shaping after adsorbing agent carrier particle in molecular sieve and the weight ratio range of choices of binding agent wider.For the present invention, under preferable case, described shaping after the preparation method of adsorbing agent carrier particle comprise: under roller forming condition, in butt, by molecular sieve and binding agent according to the weight ratio mixing of 1:0.02-0.1 and by shaping for the mixture obtained.
Described roller forming condition can be carried out with reference to prior art, and for the present invention, described roller forming condition can comprise the steps: molecular sieve and binding agent to send into after in former, then according to moulding process need to add water or do not add water carry out shaping.When the water content in molecular sieve and binding agent meets molding technological condition (water content is generally 30-50 % by weight), not needing to add water, it is shaping to carry out.When the water content in molecular sieve and binding agent does not meet the water yield needed for moulding process, when molecular sieve and binding agent are mixed, need to add a certain amount of water.The addition manner of water can have multiple, such as can enter in former at molecular sieve and binding agent and mix and carry out adding in shaping process, also can add in the mixed process of molecular sieve and binding agent before molecular sieve and binding agent enter former, in addition, water can once add enough, also can add until enough in batches.In the present invention, the concrete addition of water specifically can be selected according to the water content in the general shaping required water yield of prior art and molecular sieve of the present invention and binding agent.For the present invention, the addition of described water make conventionally to carry out shaping after, described shaping after the water content of adsorbing agent carrier particle be 30-50 % by weight.
According to the present invention, the selectable range of the kind of described molecular sieve is wider, the molecular sieve of what this area was commonly used can be used in adsorption stripping dimethyl benzene all can realize object of the present invention, for the present invention, under preferable case, described molecular sieve is one or more in A type molecular sieve, X-type molecular sieve, Y zeolite.For the present invention, further preferred described molecular sieve is X-type molecular sieve, is more preferably 13X molecular sieve.
In the present invention, the selectable range of the kind of described binding agent is wider, the binding agent that this area is commonly used all can realize object of the present invention, for the present invention, under preferable case, described binding agent is one or more in kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite, and under preferable case, described binding agent is kaolin.
According to activation method of the present invention, wherein, the granularity of molecular sieve and binding agent can be selected in relative broad range with reference to prior art, and under preferable case, the granularity of described molecular sieve is less than 1 μm, is preferably 0.5-0.7 μm; The granularity of described binding agent is less than 87 μm, and when being preferably 30-50 μm, the effect realizing object of the present invention is better.
According to the present invention, under preferable case, optionally, described shaping after the preparation method of adsorbing agent carrier particle be also included in the process of mixed molecular sieve and binding agent and add auxiliary agent, the introducing method of described auxiliary agent also can have multiple, such as can add auxiliary agent molecular sieve and binding agent being sent in the process mixed in former, also before former sent into by molecular sieve and binding agent, can introduce auxiliary agent in the process of mixed molecular sieve and binding agent, this is no longer going to repeat them.The selection of the kind of described auxiliary agent can be carried out with reference to prior art, and the preferred described auxiliary agent of the present invention is pore creating material.The present invention is not particularly limited described pore creating material, and the pore creating material that this area is commonly used all can realize object of the present invention, and such as, the trade mark can produced for the long-range Science and Technology Ltd. in Chinese and Western be that the sesbania powder of M375488 is as pore creating material.The content of described auxiliary agent, can select according to prior art, and under preferable case, in butt, the weight ratio of auxiliary agent and molecular sieve is 0.01-0.06:1.
According to activation method of the present invention, wherein, in order to strengthen described shaping after the intensity of adsorbing agent carrier particle, the method also comprise by described shaping after adsorbing agent carrier particle carry out the step of polishing.The method of described polishing can adopt and well known to a person skilled in the art various method and described polishing can be carried out in the equipment of various routine, such as, can carry out in spin pot.Described polishing process can utilize the collision between the rotation of spin pot, vibrations and particle, between particle and pot wall, friction and complete described polishing process.Described polishing process can once carry out also can repeatedly carrying out stage by stage, in order to make to obtain shaping after the intensity of adsorbing agent carrier particle better, the preferred described polishing process of the present invention adopts the mode of repeatedly carrying out stage by stage, and the time of process can be selected in relative broad range according to prior art.The breaking strength assay method of the adsorbing agent carrier particle after described shaping after polishing is with reference to CN1552515A, and represent with the percentage of damage under 250N pressure, percentage of damage is lower, and intensity is better.
Present invention also offers a kind of preparation method of paraxylene adsorbent, the method comprises the paraxylene adsorbing agent carrier through overactivation is prepared into paraxylene adsorbent, and wherein, the method for activation paraxylene adsorbing agent carrier is method as above.
According to the present invention, method paraxylene adsorbing agent carrier through overactivation being prepared into paraxylene adsorbent can adopt various method well known by persons skilled in the art, such as, under prior art conditions in-situ crystallization and cation exchange are carried out to adsorbing agent carrier.By the paraxylene adsorbing agent carrier adopting the activation method of paraxylene adsorbing agent carrier provided by the invention to activate, effectively can alleviate the shortcoming that after becoming adsorbent by molecular sieve in prior art, adsorbance obviously declines after being prepared into paraxylene adsorbent, compared with prior art can improve the adsorbance of adsorbent.In addition, the activation method of prior art can be adopted also can to adopt the activation method of paraxylene adsorbing agent carrier provided by the invention to the activation of adsorbent.
In the present invention, butt quality to refer at 600 DEG C calcination 1 hour, weight after cooling in a.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
To be described in further detail the present invention by embodiment below.
The measurement of industrial paraxylene adsorbent amount adopts toluene to characterize usually.Below in embodiment, the measurement of toluene adsorbance is under normal pressure (0.1MPa), adopts Floating method to measure the saturated extent of adsorption C of toluene, and the method comprises and being cooled after dry 2h at 500 DEG C by sample, under 35 DEG C of waters bath with thermostatic control, make N
2carry toluene vapor by sample cell to adsorption equilibrium, in system, toluene vapor relative pressure P/P0=0.5(P0 is system pressure), according to the mass change of sample before and after absorption by formula C=(M1-M0)/M0 calculates saturated extent of adsorption, in formula, M0 is sample initial mass, and M1 is quality after sample adsorption balance;
The analytical method of abrasion adopts GB-10505.2;
The moisture measurement method of the adsorbing agent carrier particle after shaping: get 2-3g sample and accurately take initial weight, put into crucible and be placed in 600 DEG C of Muffle furnace roastings to constant weight, weigh after taking out sample drying cooling, the mass fraction that the example weight of minimizing accounts for initial weight is water content;
The toluene adsorbance of adsorbance rate of descent (%)=100% × (the toluene adsorbance of molecular sieve-by molecular sieve become adsorbing agent carrier or adsorbent after toluene adsorbance)/molecular sieve;
Microwave dryer is purchased from Nanjing Di Bang microwave equipment Technology Co., Ltd.;
Vertical heater is purchased from chemical of Sinopec Nanjing Chemical Industrial Co., Ltd;
Net belt type high-temperature activation stove is purchased from Huanggang Hua Yaozhongzhou kiln Co., Ltd;
Pore creating material purchased from the long-range Science and Technology Ltd. in Chinese and Western, trade mark M375488;
Other raw materials are all from being purchased.
Embodiment 1
(1) adsorbing agent carrier grain forming
To learn from else's experience the commercially available 13X molecular screen primary powder 400Kg(water content 21 % by weight of levigate process, granularity is less than 1 μm, toluene adsorbance is 230mg/g), kaolin 20Kg(water content 22 % by weight, granularity is less than 87 μm), pore creating material 10Kg put into twin screw compounder mixing 3 hours.
Above-mentioned 50Kg mixture is put into spin pot to carry out shaping.Operating condition is: it is 40 revs/min that spin pot rotating speed controls, and adds water speed and is as the criterion with material moisture raising 3.5 % by weight per hour, when material final moisture reaches 50 % by weight, stop adding water, and keeps pot body rotating speed to be 40 revs/min, is rotated further 3.5 hours.When sphere diameter reaches 0.36-1mm, sample thief carries out polishing 2 hours, when sphere diameter reaches 1.0-1.3mm, sample thief carries out polishing 1.5 hours, then the spheroid of 0.36-1mm and the spheroid of 1.0-1.3mm is mixed by the mass ratio of 95:5 and carries out rolling shaping 0.5 hour; Obtain shaping after adsorbing agent carrier particle, the water content of the adsorbing agent carrier particle after this is shaping is 48.1 % by weight.
And so forth, carry out in 20 mouthfuls of identical spin pots, final preparation 1 ton of sample.
(2) activation of adsorbing agent carrier particle
By the adsorbing agent carrier particle after shaping for the 500Kg of above-mentioned preparation, send into and have that dried dew point is 0 DEG C, tolerance is 400Nm
3the air stream of/h, power is in the microwave dryer of 300 kilowatts, dry 60min, makes the water content of adsorbing agent carrier particle drop to 16.2 % by weight, then enters vertical heater roasting, and pass into the air stream that temperature is 550 DEG C in roasting process, tolerance is 2000Nm
3/ h, the frost point of air stream is-25 DEG C, carries out roasting 3 hours, make shaping after adsorbing agent carrier particle water content be reduced to 3.2 % by weight, obtain activate after adsorbing agent carrier particle.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Embodiment 2
(1) adsorbing agent carrier grain forming
To learn from else's experience the commercially available 13X molecular screen primary powder 400Kg(water content 21 % by weight of levigate process, granularity is less than 1 μm, toluene adsorbance is 230mg/g), kaolin 16Kg(water content 22 % by weight, granularity is less than 87 μm), pore creating material 8Kg put into twin screw compounder mixing 3 hours.
Roller forming adopts the method for embodiment 1 to carry out.
(2) activation of adsorbing agent carrier particle
By the adsorbing agent carrier particle after shaping for the 500Kg of above-mentioned preparation, send into and have that dried dew point is 20 DEG C, tolerance is 300Nm
3the air stream of/h, power is in the microwave dryer of 400 kilowatts, dry 50min, makes the water content of adsorbing agent carrier particle drop to 17.1 % by weight, then enters vertical heater roasting, and pass into the air stream that temperature is 560 DEG C in roasting process, tolerance is 1600Nm
3/ h, the dew point of air stream is-20 DEG C, carries out roasting 2 hours, make shaping after adsorbing agent carrier particle water content be reduced to 3.5 % by weight, obtain activate after adsorbing agent carrier particle.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Embodiment 3
(1) adsorbing agent carrier grain forming
To learn from else's experience the commercially available 13X molecular screen primary powder 400Kg(water content 21 % by weight of levigate process, granularity is less than 1 μm, toluene adsorbance is 230mg/g), kaolin 22Kg(water content 22 % by weight, granularity is less than 87 μm), pore creating material 12Kg put into twin screw compounder mixing 3 hours.
Roller forming adopts the method for embodiment 1 to carry out.
(2) activation of adsorbing agent carrier particle
By the adsorbing agent carrier particle after shaping for the 500Kg of above-mentioned preparation, send into and have that dried frost point is-10 DEG C, tolerance is 350Nm
3the air stream of/h, power is in the microwave dryer of 250 kilowatts, dry 70min, makes the water content of adsorbing agent carrier particle drop to 18 % by weight, then enters vertical heater roasting, and pass into the air stream that temperature is 530 DEG C in roasting process, tolerance is 1800Nm
3/ h, the dew point of air stream is-30 DEG C, carries out roasting 3 hours, make shaping after adsorbing agent carrier particle water content be reduced to 3.5 % by weight, obtain activate after adsorbing agent carrier particle.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Embodiment 4
Adsorbing agent carrier particle after 500Kg embodiment 1 prepared is shaping, sends into and has that dried dew point is 50 DEG C, tolerance is 100Nm
3the air stream of/h, power is in the microwave dryer of 400 kilowatts, dry 90min, makes the water content of adsorbing agent carrier particle drop to 16.2 % by weight, then enters vertical heater roasting, and pass into the air stream that temperature is 500 DEG C in roasting process, tolerance is 200Nm
3/ h, the dew point of air stream is 0 DEG C, carries out roasting 4 hours, make shaping after adsorbing agent carrier particle water content be reduced to 3.5 % by weight, obtain activate after adsorbing agent carrier particle.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Embodiment 5
Adsorbing agent carrier particle after 500Kg embodiment 1 prepared is shaping, sends into and has that dried dew point is 60 DEG C, tolerance is 80Nm
3the air stream of/h, power is in the microwave dryer of 500 kilowatts, dry 90min, makes the water content of adsorbing agent carrier particle drop to 16.2 % by weight, then enters vertical heater roasting, and pass into the air stream that temperature is 500 DEG C in roasting process, tolerance is 80Nm
3/ h, the dew point of air stream is 5 DEG C, carries out roasting 5 hours, make shaping after adsorbing agent carrier particle water content be reduced to 3.5 % by weight, obtain activate after adsorbing agent carrier particle.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Embodiment 6
Adopt the method for embodiment 1 prepare described shaping after adsorbing agent carrier particle and adopt the method for embodiment 1 to described shaping after adsorbing agent carrier particle activate.Unlike, in preparation process, do not add pore creating material.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Comparative example 1
Adsorbing agent carrier particle after 500Kg embodiment 1 prepared is shaping, carry out oven drying, baking temperature is 120 DEG C, drying time is 9h, makes the water content of adsorbing agent carrier particle drop to 19.8 % by weight, then enters net belt type high-temperature activation stove and carries out roasting, sintering temperature is 550 DEG C, roasting time is 2.5h, make shaping after adsorbing agent carrier particle water content be reduced to 3.5 % by weight, obtain the adsorbing agent carrier particle after roasting.
The test result of the adsorbance of the adsorbing agent carrier particle after gained roasting, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Comparative example 2
Adsorbing agent carrier particle after the 500Kg embodiment of the present invention 1 step (1) prepared is shaping activates 24 hours in 80 DEG C of nitrogen stream, obtains the adsorbing agent carrier particle after activating.
The test result of the adsorbance of adsorbing agent carrier particle after gained activation, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 1.
Table 1
Application Example 1-6 and Comparison study example 1-2
Adopt in-situ crystallization and the ion-exchange process of embodiment 1 in CN1565718A, respectively the adsorbing agent carrier particle of embodiment 1-6 and comparative example 1 and 2 is carried out in-situ crystallization and ion-exchange, obtain adsorbent.
The test result of the adsorbance of gained adsorbent, adsorbance rate of descent, percentage of damage and abrasion is as shown in table 2 respectively.
Table 2
As can be seen from table 1 and 2 result, the adsorbance of the adsorbing agent carrier adopting activation method of the present invention to prepare, percentage of damage and abrasion are better than prior art, and the adsorbance of the adsorbent prepared by adsorbing agent carrier provided by the invention, percentage of damage and abrasion are better than prior art, explanation, the adsorbing agent carrier adopting activation method of the present invention to obtain alleviates the shortcoming that prior art adsorbing agent carrier adsorbance obviously declines really, thus improve by the adsorbance of its obtained adsorbent, and take into account stronger mechanical strength.
Claims (16)
1. the activation method of a paraxylene adsorbing agent carrier, it is characterized in that, under the method is included in the existence of air stream, water content is not less than 30 % by weight shaping after adsorbing agent carrier particle carry out microwave drying, make dry after described shaping after the water content of adsorbing agent carrier particle be reduced to less than 18 % by weight; And under the existence of air stream, by dried described shaping after adsorbing agent carrier particle carry out roasting, the water content of the adsorbing agent carrier particle after to make after roasting described shaping is reduced to less than 3.5 % by weight; Described paraxylene adsorbing agent carrier is at least one in X-type molecular sieve and Y zeolite.
2. activation method according to claim 1, wherein, described water content is not less than 30 % by weight shaping after adsorbing agent carrier particle carry out microwave drying, make dry after described shaping after the water content of adsorbing agent carrier particle be reduced to 16-18 % by weight.
3. activation method according to claim 1, wherein, during microwave drying, the frost point of described air stream is greater than-50 DEG C and dew point is less than 50 DEG C; Relative to the adsorbing agent carrier particle after shaping described in 500Kg, the flow of air stream is 100-1000Nm
3/ h.
4. activation method according to claim 3, wherein, during microwave drying, the frost point of described air stream is greater than-10 DEG C and dew point is less than 20 DEG C; Relative to the adsorbing agent carrier particle after shaping described in 500Kg, the flow of air stream is 300-400Nm
3/ h.
5. according to the activation method in claim 1-4 described in any one, wherein, the power of described microwave dryer is 100-500KW, and the time of microwave drying is 30-300min.
6. activation method according to claim 5, wherein, the power of described microwave dryer is 250-400KW, and the time of microwave drying is 50-70min.
7. activation method according to claim 1, wherein, during roasting, the frost point of air stream is for being more than or equal to-80 DEG C; Relative to the adsorbing agent carrier particle after shaping described in 500Kg, the flow of air stream is 200-3000Nm
3/ h.
8. activation method according to claim 7, wherein, during roasting, the frost point of air stream is-20 DEG C to-30 DEG C; Relative to the adsorbing agent carrier particle after shaping described in 500Kg, the flow of air stream is 1600-2000Nm
3/ h.
9. according to the activation method in claim 1,2,7 and 8 described in any one, wherein, the temperature of roasting is 500-650 DEG C; The time of roasting is 1-5h.
10. activation method according to claim 9, wherein, the temperature of roasting is 530-560 DEG C; The time of roasting is 2-3h.
11. activation methods according to claim 1, wherein, before drying, described shaping after the water content of adsorbing agent carrier particle be 30-50 % by weight.
12. activation methods according to claim 1, wherein, described shaping after the preparation method of adsorbing agent carrier particle comprise: under roller forming condition, in butt, by molecular sieve and binding agent according to the weight ratio mixing of 1:0.02-0.1 and by shaping for the mixture obtained.
13. activation methods according to claim 12, wherein, the granularity of described molecular sieve is less than 1 μm, and the granularity of described binding agent is less than 87 μm.
14. activation methods according to claim 12, wherein, described shaping after the preparation method of adsorbing agent carrier particle also comprise: add auxiliary agent when mixed molecular sieve and binding agent, wherein, in butt, the weight ratio of auxiliary agent and molecular sieve is 0.01-0.06:1.
15. according to the activation method in claim 12-14 described in any one, wherein, the method also comprise by described shaping after adsorbing agent carrier particle carry out the step of polishing.
The preparation method of 16. 1 kinds of paraxylene adsorbents, the method comprises the paraxylene adsorbing agent carrier through overactivation is prepared into paraxylene adsorbent, it is characterized in that, the method for activation paraxylene adsorbing agent carrier is the method in claim 1-15 described in any one.
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| US20110237426A1 (en) * | 2010-03-25 | 2011-09-29 | Ngk Industries, Ltd. | Manufacturing method of zeolite structure |
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| US20110237426A1 (en) * | 2010-03-25 | 2011-09-29 | Ngk Industries, Ltd. | Manufacturing method of zeolite structure |
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