CN103566888A - 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 preparation method of activation method and a kind of paraxylene adsorbent of paraxylene adsorbing agent carrier.
Background technology
Paraxylene (PX) is important basic chemical industry raw material, industrial normally separated acquisition from the mixed C 8 aromatics that contains ethylbenzene, paraxylene, meta-xylene and ortho-xylene.Because four kinds of C8 aronmatic boiling points are close, adopt conventional rectifying mode to be difficult to separated, at present, industrial employing isomerization-adsorptive separation technology is produced 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, claims again molecular sieve; Synthetic resin.Research for paraxylene adsorbent mainly concentrates on adsorbent of molecular sieve.The method of 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, and still the special research for carrier rarely has report.
CN1565718A discloses a kind of paraxylene adsorbent and preparation method, the method comprises: NaX or NaKX zeolite powder that (1) is 0.1-0.4 micron by size of microcrystal mix by the mass ratio of 88-95:5-12 with kaolin, on water spray limit, rolling former top, rolls and makes it balling-up; (2) bead of above-mentioned rolling moulding is sieved into the bead of 0.60-0.80 millimeter and 0.35-0.60 millimeter, then by the mass ratio of 20-30:70-80, mixes the shaping of rolling, dry, roasting; (3) by the bead after roasting with the mixed solution of sodium hydroxide solution or NaOH and sodium metasilicate 90-100 ℃ of processing, making kaolin in-situ crystallization is wherein X-type zeolite, then dry, roasting; (4) with the soluble-salt solution of barium or the soluble-salt solution of potassium and barium, carry out cation exchange, then wash, activate.Described activation generally be take hot-air or nitrogen as medium is to remove moisture unnecessary in adsorbent, and described activation temperature is 80-200 ℃, and the time is 24-72 hour.This activating process is consuming time longer, and activation efficiency is lower.
In addition, in preparing the method for adsorbent of molecular sieve, ubiquity a problem, and the active component using molecular sieve as adsorbent is prepared into after adsorbent exactly, has the obvious shortcoming declining of adsorbance of molecular sieve.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of activation method and a kind of paraxylene adsorbent of paraxylene adsorbing agent carrier, the method can effectively be alleviated molecular sieve and become the shortcoming that adsorbance obviously declines after adsorbing agent carrier, thereby effectively alleviate by molecular sieve, become the shortcoming that adsorbance obviously declines after adsorbent, can improve thus the adsorbance of paraxylene adsorbent.
The present inventor finds in experiment, at molecular sieve, become the adsorbance of carrier in adsorbent process to decline obviously, by improving the activation method by the adsorbing agent carrier of molecular sieve, alleviation is become the obvious decline of adsorbance after adsorbing agent carrier by molecular sieve, and improve the adsorbance of adsorbing agent carrier, thereby can effectively alleviate by molecular sieve, become the shortcoming that adsorbance obviously declines after adsorbent.
For above-mentioned purpose, the invention provides a kind of activation method of paraxylene adsorbing agent carrier, wherein, the method is included under the existence of air stream, adsorbing agent carrier particle water content being not less than after the moulding of 30 % by weight carries out microwave drying, the water content of the adsorbing agent carrier particle after dry rear described moulding is reduced to below 18 % by weight, preferably 16-18 % by weight; And under the existence of air stream, the adsorbing agent carrier particle after dried described moulding is carried out to roasting, the water content of the adsorbing agent carrier particle after the described moulding after roasting is reduced to below 3.5 % by weight.
The present invention also provides a kind of preparation method of paraxylene adsorbent, and 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 finds by a large amount of experiments, under the existence of air stream, by microwave drying and roasting, can effectively alleviate the obvious shortcoming declining of adsorbance of the adsorbing agent carrier particle making.Infer that this may be heated evenly because microwave drying can make adsorbing agent carrier particle, and in the process of dry and roasting, there is the existence of air stream, can take away as early as possible water vapour, reduce the time that water vapour contacts with adsorbing agent carrier particle, especially in roasting process, can reduce as much as possible high temperature air stream and cause molecular sieve to stand the impact of high-temperature water heat ageing with the existence of steam, thereby alleviate molecular sieve, make the defect that adsorbance obviously declines after adsorbing agent carrier.
Under preferable case of the present invention, the air stream when to microwave drying and roasting is controlled, and during as microwave drying, the frost point of described air stream is greater than-50 ℃ and dew point and is less than 50 ℃, is preferably frost point and is greater than-10 ℃ and dew point and be less than 20 ℃; During roasting, the frost point of air stream, for being more than or equal to-80 ℃, is preferably-20 ℃ to-30 ℃.Air stream while controlling microwave drying and roasting, in above-mentioned scope, can further be alleviated molecular sieve and make the defect that adsorbance obviously declines after adsorbing agent carrier.
Activation method provided by the invention has been realized the effective activation to adsorbing agent carrier by the improvement dry, roasting technique of the adsorbing agent carrier to after moulding, effectively alleviated in prior art by molecular sieve and become the shortcoming that adsorbance obviously declines after adsorbing agent carrier, also alleviated in prior art by molecular sieve and become the shortcoming that adsorbance obviously declines after adsorbent, compared with prior art improved the adsorbance of adsorbent, and can make the adsorbent making take into account stronger mechanical strength.In addition, the method for microwave drying that the present invention adopts, has not only improved production efficiency, and economic environmental protection, method simply, easily operation.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the activation method of described paraxylene adsorbing agent carrier is included under the existence of air stream, adsorbing agent carrier particle water content being not less than after the moulding of 30 % by weight carries out microwave drying, the water content of the adsorbing agent carrier particle after dry rear described moulding is reduced to below 18 % by weight, preferably 16-18 % by weight; And under the existence of air stream, the adsorbing agent carrier particle after dried described moulding is carried out to roasting, the water content of the adsorbing agent carrier particle after the described moulding after roasting is reduced to below 3.5 % by weight.
In the present invention, after microwave drying, when the water content of the adsorbing agent carrier particle after described moulding can cause roasting below higher than 18 % by weight, molecular sieve adsorbance declines too fast; And the water content of the adsorbing agent carrier particle after the described moulding after roasting can cause reducing the absorption property of adsorbent higher than 3.5 % by weight; Therefore, the water content after controlling microwave drying and the water content after roasting, in above-mentioned scope, can effectively be alleviated molecular sieve and make the defect that adsorbance obviously declines after adsorbent.
According to preceding method of the present invention, can realize goal of the invention of the present invention, in order better to realize goal of the invention of the present invention, for the present invention, under preferable case, the air stream using during microwave drying, can be dried processing according to prior art, and the frost point of dried air stream is greater than, and-50 ℃ and dew point are less than 50 ℃, more preferably the frost point of described air stream is greater than-10 ℃ and dew point and is less than 20 ℃, realizes effect of the present invention better.While carrying out microwave drying, can select according to the quality of the adsorbing agent carrier particle after described moulding the flow of air stream, and the quality of adsorbing agent carrier particle and the flow of air stream after described moulding can be selected in relative broad range, as long as make the water content of the adsorbing agent carrier particle after dry rear described moulding be reduced to 18 % by weight below, conventionally can be reduced to 16-18 % by weight.Under preferable case, with respect to the adsorbing agent carrier particle after moulding described in 500Kg, the flow of air stream is 100-1000Nm
3/ h, more preferably 300-400Nm
3/ h.
According to activation method of the present invention, the present invention does not have special requirement to carrying out the equipment of microwave drying, the time of microwave drying is not had to special requirement yet, as long as make the water content of the adsorbing agent carrier particle after dry rear described moulding be reduced to 18 % by weight below, conventionally can be reduced to 16-18 % by weight.Under preferable case, the power of the equipment of described microwave drying is 100-500KW, more preferably 250-400KW; The time of microwave drying is 30-300min, more preferably 50-70min.
According to activation method of the present invention, in order better to realize goal of the invention of the present invention, for the present invention, under preferable case, the air stream using during roasting, can be dried processing according to prior art, makes the frost point of dried air stream for being more than or equal to-80 ℃, more preferably-20 ℃ to-30 ℃, realize effect of the present invention better.While carrying out roasting, can select according to the quality of the adsorbing agent carrier particle after dried described moulding the flow of air stream, and the quality of adsorbing agent carrier particle and the flow of air stream after dried described moulding can be selected in relative broad range, as long as make the water content of the adsorbing agent carrier particle after described moulding after roasting be reduced to 3.5 % by weight below.Under preferable case, with respect to the adsorbing agent carrier particle after moulding 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, as long as can make the water content of the adsorbing agent carrier particle after described moulding after roasting be reduced to 3.5 % by weight below.Under preferable case, the temperature of roasting is 500-650 ℃, more preferably 530-560 ℃; The time of roasting is 1-5h, 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 ventilation stream, is preferably vertical heater.
According to activation method of the present invention, generally, before being dried, the water content of the adsorbing agent carrier particle after described moulding is not less than 30 % by weight, for example, according to conventional method, carry out after moulding, the water content of the adsorbing agent carrier particle after described moulding is 30-50 % by weight.
According to the present invention, the preparation method of the adsorbing agent carrier particle after described moulding can carry out with reference to prior art, for example generally, the preparation method of the adsorbing agent carrier particle after described moulding comprises molecular sieve and binding agent is mixed, and optional wider range of weight ratio of the molecular sieve in the adsorbing agent carrier particle after described moulding and binding agent.For the present invention, under preferable case, the preparation method of the adsorbing agent carrier particle after described moulding comprises: under roller forming condition, in butt, molecular sieve and binding agent are mixed according to the weight ratio of 1:0.02-0.1 and by the mixture moulding obtaining.
Described roller forming condition can be carried out with reference to prior art, and for the present invention, then described roller forming condition need to add water or not add water according to moulding process and carry out moulding after can comprising the steps: that molecular sieve and binding agent are sent in former.When the water content in molecular sieve and binding agent meets molding technological condition (water content is generally 30-50 % by weight), do not need to add water and can carry out moulding.When the water content in molecular sieve and binding agent does not meet the required water yield of 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, for example can in entering former, molecular sieve and binding agent mix and carry out to add in the process of moulding, also can before entering former, molecular sieve and binding agent add in the mixed process of molecular sieve and binding agent, in addition, water can once add enough, also can add until enough in batches.In the present invention, the concrete addition of water can specifically be selected according to the required water yield of the general moulding of prior art and the water content in molecular sieve of the present invention and binding agent.For the present invention, the addition of described water makes to carry out after moulding according to conventional method, and the water content of the adsorbing agent carrier particle after described moulding is 30-50 % by weight.
According to the present invention, the selectable range of the kind of described molecular sieve is wider, the conventional molecular sieve that can be used in adsorption stripping dimethyl benzene in this area all can be realized 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, more preferably 13X molecular sieve.
In the present invention, the selectable range of the kind of described binding agent is wider, the conventional binding agent in this area all can be realized 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 with reference to prior art in relative broad range, and under preferable case, the granularity of described molecular sieve is less than 1 μ m, is preferably 0.5-0.7 μ m; The granularity of described binding agent is less than 87 μ m, and while being preferably 30-50 μ m, the effect that realizes object of the present invention is better.
According to the present invention, under preferable case, optionally, the preparation method of the adsorbing agent carrier particle after described moulding is also included in the process of mixed molecular sieve and binding agent and adds auxiliary agent, the introducing method of described auxiliary agent also can have multiple, for example, in the process that can mix, add auxiliary agent in molecular sieve and binding agent are sent into former, also can before molecular sieve and binding agent are sent into former, in the process of mixed molecular sieve and binding agent, introduce auxiliary 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 conventional pore creating material in this area all can be realized object of the present invention, and for example, the sesbania powder that the trade mark that can produce for the long-range Science and Technology Ltd. in Chinese and Western is 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 the intensity of the adsorbing agent carrier particle after described moulding, the method also comprises the step of the adsorbing agent carrier particle after described moulding being carried out to polishing.The method of described polishing can adopt and well known to a person skilled in the art that the whole bag of tricks and described polishing can carry out in the equipment of various routines, for example, can in spin pot, carry out.Described polishing process can utilize between rotation, vibrations and the particle of spin pot, the collision 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, for the intensity of the adsorbing agent carrier particle after the moulding that makes to make better, the preferred described polishing process of the present invention adopts the mode of repeatedly carrying out stage by stage, and the time of processing can be selected according to prior art in relative broad range.The breaking strength assay method of the adsorbing agent carrier particle after the described moulding after polishing, with reference to CN1552515A, represents with the percentage of damage under 250N pressure, and percentage of damage is lower, and intensity is better.
The present invention also provides a kind of preparation method of paraxylene adsorbent, and 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, the method that paraxylene adsorbing agent carrier through overactivation is prepared into paraxylene adsorbent can adopt the whole bag of tricks well known by persons skilled in the art, for example, under prior art condition, adsorbing agent carrier is carried out to in-situ crystallization and cation exchange.By adopting the paraxylene adsorbing agent carrier of the activation method activation of paraxylene adsorbing agent carrier provided by the invention, be prepared into can effectively alleviate after paraxylene adsorbent in prior art by molecular sieve and become the shortcoming that adsorbance obviously declines after adsorbent, compared with prior art can improve the adsorbance of adsorbent.In addition, to the activation of adsorbent, can adopt the activation method of prior art also can adopt the activation method of paraxylene adsorbing agent carrier provided by the invention.
In the present invention, butt quality refers at 600 ℃ calcination 1 hour, cooled weight in drier.
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 characterictic described in the above-mentioned specific embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, 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 the present invention, be described in further detail by embodiment below.
The measurement of industrial paraxylene adsorbent adsorbance adopts toluene to characterize conventionally.In embodiment, the measurement of toluene adsorbance is under normal pressure (0.1MPa) below, adopts Floating method to measure the saturated extent of adsorption C of toluene, and the method comprises sample cooling after dry 2h at 500 ℃, under 35 ℃ of waters bath with thermostatic control, makes N
2carry toluene steam by sample cell to adsorption equilibrium, in system, toluene vapor phase is system pressure to pressure P/P0=0.5(P0), 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 equilibrium;
The analytical method of abrasion adopts GB-10505.2;
The moisture measurement method of the adsorbing agent carrier particle after moulding: get 2-3g sample and accurately take initial weight, put into crucible and be placed in 600 ℃ of Muffle furnace roastings to constant weight, after taking-up sample drying is cooling, weigh, 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-molecular sieve is become to toluene adsorbance after adsorbing agent carrier or adsorbent)/molecular sieve;
Microwave dryer is purchased from microwave equipment technology Co., Ltd of Nanjing Supreme Being nation;
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 is 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
Learnt from else's experience commercially available 13X molecular screen primary powder 400Kg(water content 21 % by weight of levigate processing, granularity is less than 1 μ m, toluene adsorbance is 230mg/g), kaolin 20Kg(water content 22 % by weight, granularity is less than 87 μ m), pore creating material 10Kg puts into twin screw compounder and mixes 3 hours.
Above-mentioned 50Kg mixture is put into spin pot and carry out moulding.Operating condition is: it is 40 revs/min that spin pot rotating speed is controlled, 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, stops adding water, and keeping pot body rotating speed is 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 is mixed to the shaping 0.5 hour of rolling with the spheroid of 1.0-1.3mm by the mass ratio of 95:5; Obtain the adsorbing agent carrier particle after moulding, the water content of the adsorbing agent carrier particle after this moulding is 48.1 % by weight.
And so forth, in 20 mouthfuls of identical spin pots, carry out, finally prepare 1 ton of sample.
(2) activation of adsorbing agent carrier particle
By the adsorbing agent carrier particle after the 500Kg moulding of above-mentioned preparation, send into that to have the dew point being dried be that 0 ℃, tolerance are 400Nm
3the air stream of/h, power is in the microwave dryer of 300 kilowatts, and dry 60min, makes the water content of adsorbing agent carrier particle drop to 16.2 % by weight, then enters vertical heater roasting, passes into temperature and be the air stream of 550 ℃ in roasting process, and tolerance is 2000Nm
3/ h, the frost point of air stream is-25 ℃, carries out roasting 3 hours, makes the adsorbing agent carrier particle water content after moulding be reduced to 3.2 % by weight, the adsorbing agent carrier particle after being activated.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Embodiment 2
(1) adsorbing agent carrier grain forming
Learnt from else's experience commercially available 13X molecular screen primary powder 400Kg(water content 21 % by weight of levigate processing, granularity is less than 1 μ m, toluene adsorbance is 230mg/g), kaolin 16Kg(water content 22 % by weight, granularity is less than 87 μ m), pore creating material 8Kg puts into twin screw compounder and mixes 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 the 500Kg moulding of above-mentioned preparation, send into that to have the dew point being dried be that 20 ℃, tolerance are 300Nm
3the air stream of/h, power is in the microwave dryer of 400 kilowatts, and dry 50min, makes the water content of adsorbing agent carrier particle drop to 17.1 % by weight, then enters vertical heater roasting, passes into temperature and be the air stream of 560 ℃ in roasting process, and tolerance is 1600Nm
3/ h, the dew point of air stream is-20 ℃, carries out roasting 2 hours, makes the adsorbing agent carrier particle water content after moulding be reduced to 3.5 % by weight, the adsorbing agent carrier particle after being activated.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Embodiment 3
(1) adsorbing agent carrier grain forming
Learnt from else's experience commercially available 13X molecular screen primary powder 400Kg(water content 21 % by weight of levigate processing, granularity is less than 1 μ m, toluene adsorbance is 230mg/g), kaolin 22Kg(water content 22 % by weight, granularity is less than 87 μ m), pore creating material 12Kg puts into twin screw compounder and mixes 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 the 500Kg moulding of above-mentioned preparation, send into have the frost point that was dried for-10 ℃, tolerance be 350Nm
3the air stream of/h, power is in the microwave dryer of 250 kilowatts, and dry 70min, makes the water content of adsorbing agent carrier particle drop to 18 % by weight, then enters vertical heater roasting, passes into temperature and be the air stream of 530 ℃ in roasting process, and tolerance is 1800Nm
3/ h, the dew point of air stream is-30 ℃, carries out roasting 3 hours, makes the adsorbing agent carrier particle water content after moulding be reduced to 3.5 % by weight, the adsorbing agent carrier particle after being activated.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Embodiment 4
By the adsorbing agent carrier particle after the 500Kg moulding of embodiment 1 preparation, send into that to have the dew point being dried be that 50 ℃, tolerance are 100Nm
3the air stream of/h, power is in the microwave dryer of 400 kilowatts, and dry 90min, makes the water content of adsorbing agent carrier particle drop to 16.2 % by weight, then enters vertical heater roasting, passes into temperature and be the air stream of 500 ℃ in roasting process, and tolerance is 200Nm
3/ h, the dew point of air stream is 0 ℃, carries out roasting 4 hours, makes the adsorbing agent carrier particle water content after moulding be reduced to 3.5 % by weight, the adsorbing agent carrier particle after being activated.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Embodiment 5
By the adsorbing agent carrier particle after the 500Kg moulding of embodiment 1 preparation, send into that to have the dew point being dried be that 60 ℃, tolerance are 80Nm
3the air stream of/h, power is in the microwave dryer of 500 kilowatts, and dry 90min, makes the water content of adsorbing agent carrier particle drop to 16.2 % by weight, then enters vertical heater roasting, passes into temperature and be the air stream of 500 ℃ in roasting process, and tolerance is 80Nm
3/ h, the dew point of air stream is 5 ℃, carries out roasting 5 hours, makes the adsorbing agent carrier particle water content after moulding be reduced to 3.5 % by weight, the adsorbing agent carrier particle after being activated.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Embodiment 6
The adsorbing agent carrier particle of the method that adopts the method for embodiment 1 to prepare the adsorbing agent carrier particle after described moulding and adopt embodiment 1 after to described moulding activates.Different, in preparation process, do not add pore creating material.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Comparative example 1
By the adsorbing agent carrier particle after the 500Kg moulding of embodiment 1 preparation, carry out oven drying, baking temperature is 120 ℃, be 9h drying time, 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 carry out roasting, sintering temperature is 550 ℃, roasting time is 2.5h, makes the adsorbing agent carrier particle water content after moulding be reduced to 3.5 % by weight, obtains 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 500Kg moulding prepared by the embodiment of the present invention 1 step (1) activates 24 hours, the adsorbing agent carrier particle after being activated in 80 ℃ of nitrogen streams.
The test result of adsorbance, adsorbance rate of descent, percentage of damage and the abrasion of the adsorbing agent carrier particle after gained activation is as shown in table 1.
Table 1
Application Example 1-6 and application comparative example 1-2
The in-situ crystallization and the ion-exchange process that adopt embodiment 1 in CN1565718A, carry out in-situ crystallization and ion-exchange by the adsorbing agent carrier particle of embodiment 1-6 and comparative example 1 and 2 respectively, obtains 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
From the result of table 1 and 2, can find out, adopt adsorbance, percentage of damage and the abrasion of the adsorbing agent carrier that activation method of the present invention prepares to be better than prior art, and the adsorbance of the adsorbent of being prepared by adsorbing agent carrier provided by the invention, percentage of damage and abrasion are better than prior art, explanation, adopt the adsorbing agent carrier that activation method of the present invention obtains really to alleviate the shortcoming that prior art adsorbing agent carrier adsorbance obviously declines, thereby improved the adsorbance of the adsorbent being made by it, and taken into account stronger mechanical strength.
Claims (11)
1. the activation method of a paraxylene adsorbing agent carrier, it is characterized in that, the method is included under the existence of air stream, adsorbing agent carrier particle water content being not less than after the moulding of 30 % by weight carries out microwave drying, the water content of the adsorbing agent carrier particle after dry rear described moulding is reduced to below 18 % by weight, preferably 16-18 % by weight; And under the existence of air stream, the adsorbing agent carrier particle after dried described moulding is carried out to roasting, the water content of the adsorbing agent carrier particle after the described moulding after roasting is reduced to below 3.5 % by weight.
2. activation method according to claim 1, wherein, during microwave drying, the frost point of described air stream is greater than-50 ℃ and dew point and is less than 50 ℃, is preferably frost point and is greater than-10 ℃ and dew point and be less than 20 ℃; With respect to the adsorbing agent carrier particle after moulding described in 500Kg, the flow of air stream is 100-1000Nm
3/ h, is preferably 300-400Nm
3/ h.
3. activation method according to claim 1 and 2, wherein, the power of described microwave dryer is 100-500KW, is preferably 250-400KW, the time of microwave drying is 30-300min, is preferably 50-70min.
4. activation method according to claim 1, wherein, during roasting, the frost point of air stream, for being more than or equal to-80 ℃, is preferably-20 ℃ to-30 ℃; With respect to the adsorbing agent carrier particle after moulding described in 500Kg, the flow of air stream is 200-3000Nm
3/ h, is preferably 1600-2000Nm
3/ h.
5. according to the activation method described in claim 1 or 4, wherein, the temperature of roasting is 500-650 ℃, is preferably 530-560 ℃; The time of roasting is 1-5h, is preferably 2-3h.
6. activation method according to claim 1, wherein, dry before, the water content of the adsorbing agent carrier particle after described moulding is 30-50 % by weight.
7. activation method according to claim 1, wherein, the preparation method of the adsorbing agent carrier particle after described moulding comprises: under roller forming condition, in butt, molecular sieve and binding agent are mixed according to the weight ratio of 1:0.02-0.1 and by the mixture moulding obtaining.
8. activation method according to claim 7, wherein, the granularity of described molecular sieve is less than 1 μ m, and the granularity of described binding agent is less than 87 μ m.
9. activation method according to claim 7, wherein, the preparation method of the adsorbing agent carrier particle after described moulding also comprises: when mixed molecular sieve and binding agent, add auxiliary agent, wherein, in butt, the weight ratio of auxiliary agent and molecular sieve is 0.01-0.06:1.
10. according to the activation method described in any one in claim 7-9, wherein, the method also comprises the step of the adsorbing agent carrier particle after described moulding being carried out to polishing.
The preparation method of 11. 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 described in any one in claim 1-10.
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| CN109772261A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | 5A adsorbent of molecular sieve and its preparation method and application |
| CN110961087A (en) * | 2019-11-26 | 2020-04-07 | 浙江海洋大学 | PX adsorbent and preparation method thereof |
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| CN110961087A (en) * | 2019-11-26 | 2020-04-07 | 浙江海洋大学 | PX adsorbent and preparation method thereof |
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