CN1552515A - Paraxylene adsorbent and preparing method thereof - Google Patents
Paraxylene adsorbent and preparing method thereof Download PDFInfo
- Publication number
- CN1552515A CN1552515A CNA031379176A CN03137917A CN1552515A CN 1552515 A CN1552515 A CN 1552515A CN A031379176 A CNA031379176 A CN A031379176A CN 03137917 A CN03137917 A CN 03137917A CN 1552515 A CN1552515 A CN 1552515A
- Authority
- CN
- China
- Prior art keywords
- quality
- kaolin
- sorbent material
- zeolite
- exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
An adsorbent for adsorbing p-xylene from mixed C8 arylhydrocarbon is composed of the adsorptive active component chosen from Ba or Ba and K exchange X zeolite to Y zeolite (88-95 mass%) and the kaolinite. Its advantages are high adsorption capacity and high adsorption selectivity.
Description
Technical field
The present invention relates to a kind of p-Xylol sorbent material, specifically, is the sorbent material and the preparation method of p-Xylol in a kind of fractionation by adsorption xylol.
Background technology
P-Xylol (PX) is from petrochemical complex basic material-mixed C
8Aromatic hydrocarbons, it is the important products of ethene and reformer.Mixed C
8Aromatic hydrocarbons comprises: p-Xylol (PX), m-xylene (MX), o-Xylol (OX) and four isomer of ethylbenzene (EB), its boiling-point difference is very little, particularly, m-xylene boiling point is only differed from 0.6 ℃, the industrial adsorption separating method production high purity p-Xylol that generally adopts.Adsorption separation technology system cooperates simulation moving-bed continuous countercurrent separating technology to constitute by zeolite adsorbents, and its core is the development and application of high-efficiency adsorbent.In adsorption tower, utilize the sorbent material selection adsorptive power different, through countercurrent mass transfer exchange repeatedly to each isomer of xylol, it is dense that p-Xylol is constantly carried, carry dense p-Xylol by the strippant desorb again, the rectifying Extract reclaims strippant, obtains the high purity p-Xylol.The p-Xylol purity of producing by this method can reach 99.8%, yield can reach 98%, has become the main developing direction of p-Xylol separating technology.
The forming method of sorbent material be sorbent material preparation gordian technique it.EP0507122A mentions zeolite powder and alumino silica gel is blended in moulding in the oleyl amine post, USP3878127, USP3878129 and CN1275926A, CN1347339A etc. make the particulate state agglomerate with zeolite powder and kaolin, and its shape can be bead, thin slice or extrudes particulate.
Oleyl amine post method of forming complex process, cost height in the above-mentioned technology; Extrude, suppress the bead sorbent material that is difficult to prepare easily the different grain size distribution.And rolling balling is more easy to operate, and can prepare the sorbent material that is suitable for the liquid phase adsorption separation p-Xylol.General rolling ball method is master batch is constantly contacted in rolling, adheres to powder and to make the particle cluster fusion big, used powder mixed once makes, particle identical with composition all the time powder in aggregation procedure contacts, so that inside and outside even, but the granulation mass density that obtains like this is lower under same clay content.
Summary of the invention
The purpose of this invention is to provide a kind of sorbent material and preparation method of fractionation by adsorption p-Xylol, this sorbent material has bigger loading capacity, preferably adsorption selectivity, rate of mass transfer and low ash content.
Sorbent material provided by the invention comprises that massfraction is 88～95% adsorption activity component and 5～12% kaolin, and described adsorption activity component is selected from the X zeolite or the Y zeolite of Ba or Ba and K exchange, and the bright basic bulk density of sorbent material is not less than 0.84 gram per centimeter
3
The present invention adopts the method moulding of substep batch mixing spin, and the sorbent material of preparation has higher bulk density, and crushing strength might as well.Because sorbent material density height, therefore filling quantity increase in the equal volume, and the sorbent material pore distribution also more is tending towards rationally, so sorbent material of the present invention has higher loading capacity and rate of mass transfer preferably.
Embodiment
The adsorptive power of sorbent material mainly depends on the ratio of wherein contained active ingredient, and active component content is high more, and degree of crystallinity is high more, and adsorptive power is big more.But consider that the fractionation by adsorption operation time need use the sorbent material of moulding, and sorbent material needs certain withstand voltage properties after the moulding, the bed layer pressure that produces when adapting to adsorption operations.Thereby the binding agent of some amount arranged all in the sorbent material of moulding.Binding agent is a kaolin in the sorbent material of the present invention, preferred 5～10 quality % of its content, active ingredient is selected from the X zeolite or the Y zeolite of Ba or Ba and K exchange, and just the cation-bit of described zeolite is occupied separately by the Ba ion, or is occupied jointly by Ba ion and potassium ion.Preferred active ingredient is BaX or BaKX.
When the adsorbent activity component was BaKX or BaKY, the mol ratio of Ba and K was 10～40.
The silicon oxide of described X zeolite and the mol ratio of aluminum oxide, promptly silica alumina ratio is 2.0～3.0, and is preferred 2.0～2.5, the silica alumina ratio of Y zeolite is 4.0～8.0, preferred 4.0～6.0.
The content of crystallization material is at least 90 quality % in the described kaolin, the crystallization material that contains in the kaolin is generally kandite, comprise kaolinite, dickite, nacrite, refractory pebbles and halloysite, wherein halloysite is the kaolinite that contains middle water, because the existence of middle water, the crystalline structure layer curls and forms the tubulose form, thereby different with kaolinic laminate structure.Crystalline mineral such as kaolinite is many in the kaolin, will help making its in-situ crystallization change the X zeolite into by alkaline purification, thereby increase the content of active ingredient in the sorbent material.
The kandite content that contains in the preferred kaolin of the present invention is at least 90 quality %, can be above-mentioned kandite or their mixture, the mixture of preferred kaolinite or kaolinite and halloysite, wherein kaolinite content is 75～95 quality %, and halloysite content is 5～15 quality %.
The preferred roller forming of the forming method of described sorbent material, the spheroidal adsorbent size distribution that makes is 297～740 microns, wherein 297～590 microns spherolite accounts for 65～70 quality % of total amount.
Preferred 0.84～0.90 gram per centimeter of the bright basic bulk density of sorbent material of the present invention
3, more preferably 0.84～0.88 gram per centimeter
3Higher bright basic bulk density helps improving the sorbent material loadings of unit volume, under the identical condition of adsorption selectivity, improves total adsorptive power of p-Xylol, thereby increases the processing power of device.
The present invention adopts the method for rolling moulding to prepare sorbent material, and its ultimate principle is a powder after wetting, and can reunite under the effect of liquid bridge surface tension and capillary force forms micronucleus, and the trend of the more little this nucleation of powder granule is obvious more.The micronucleus bed of material of reuniting continuously turns round in the equipment of rotational forming, and under the effect of frictional force and rolling impact power, little by little also poly-and covering becomes bigger spherolite.
Particularly, preparation of adsorbent method of the present invention comprises the steps:
(1) preparation master batch: with X zeolite or Y zeolite and kaolin mixing, make particle diameter and be 0.180～0.190 millimeter master batch, kaolin content is less than 5 quality % in the master batch;
(2) roller forming: the rolling disk that master batch is placed roller press, prepare X zeolite or Y zeolite and kaolinic powder carries out roller forming in batches, kaolin content is 5～7 quality % in the used powder of spin initial stage, kaolin content is 8～10 quality % in the spin used powder in mid-term, kaolin content is 11～13 quality % in the used powder of spin later stage, the water yield that each phase spin sprays into is 15～20% of a used powder quality, and spin initial stage, mid-term, used powder quality ratio of later stage are 1: 1.5～1.9: 0.5～0.9; The bead of choosing particle diameter and be 0.35～0.80 millimeter carries out drying, 500～700 ℃ of roastings;
(3) preparation sorbent material: the bead after the roasting is carried out the exchange of barium ion exchange or barium and potassium ion after with the alkaline solution dip treating again, exchange after drying.
When preparing master batch in the described method, the particle diameter of kaolin and used zeolite all should be as much as possible little, and wherein kaolinic median size is 57～74 microns, preferred 57～62 microns.The preparation master batch can adopt rolling balling.Preferred 4～5 quality % of kaolin content in the master batch.
Preferred 75～95 quality % of kaolinite mineral content in the described kaolin wherein also can contain the halloysite of 5～15 quality %.
(2) going on foot described roller forming, is that master batch is constantly contacted with powder in roller press, assembles the process of growing up, and needs water spray constantly during spin, so that spherome surface is wetting, adheres to powder.Described powder is zeolite and kaolinic mixture, divides three times and adds in the rolling disk, and the kaolin content that at every turn adds powder is all different, and it is reinforced to be fed to the later stage by the initial stage, and kaolinic content increases gradually in the powder.
The pellet that obtains after the later stage spin need screen, with sieve particle diameter be that 0.35～0.80 millimeter bead carries out drying, roasting.Drying temperature is 80～120 ℃, preferred 6～12 hours of time, preferred 4～8 hours of roasting time.Screening back is returned rolling disk less than 0.35 millimeter particle and is continued to grow up, and can be used as the mid-term powder after pulverizing greater than 0.80 millimeter particle and continues to use.
(3) step is that small spherical particles after the moulding is carried out alkaline purification, so that wherein part kaolin carries out in-situ crystallization and changes zeolite into, increases active component content.The preferred sodium hydroxide solution of described alkaline solution, its concentration are 1.5～4.0 mol, preferred 1.6～2.0 mol, and alkali lye is 1.1～2.0: 1 with the liquid/solid volume ratio of bead during processing, treatment temp is 90～95 ℃, preferred 0.5～2.0 hour of time.
Bead after the alkaline purification need carry out cationic exchange just can make sorbent material.Cationic exchange is used the soluble salt solution of barium, potassium, the preferred nitrate of baryta of barium salt and sylvite, bariumchloride, saltpetre or Repone K.The temperature of carrying out ion-exchange is 60～160 ℃, preferred 80～110 ℃.The ratio of sodium ion mole number in the positively charged ion mole number of exchange in the liquid and the zeolite, i.e. exchange is than being 1.5～2.0.If when containing barium and potassium simultaneously in the sorbent material, the mixing solutions that can prepare barium salt and sylvite in return liquid carries out barium, potassium ion exchange simultaneously, also can carry out the barium exchange with barium salt solution earlier, carries out the potassium exchange with potassium salt soln again.Exchange back was 100～120 ℃ of dryings 6～24 hours.
The also selective and desorb speed of the important performance indexes of sorbent material except that loading capacity.Selectivity is the ability of each isomer component in the separating mixed dimethyl.Selectivity when reaching adsorption equilibrium, the ratio of the ratio of the quality of these two kinds of components or volume in the ratio of the quality of two kinds of components or volume and the non-absorption mutually in the absorption mutually.The condition that described adsorption equilibrium is determined is C
8Aromatic hydrocarbons is with after sorbent material in the absorption celebrating contact, i.e. absorption mutually and the state when between the non-absorption phase component net transfer not taking place.Selectivity β is calculated by following formula:
C and D desire to carry out isolating two kinds of components, A with what quality or volume fraction were represented in the formula
CAnd A
DThe quality or the volume fraction of C, D two components during expression is adsorbed mutually respectively, U
C, U
DQuality or the volume fraction of representing C during non-absorption mutually, D two components respectively.When two kinds of components selection β ≈ 1, there is not wherein a kind of preferentially adsorbed of component in the degree that they are adsorbed each other or are not adsorbed much at one.When β＞1 or＜1 the time, wherein a kind of component promptly appears by the separable process of preferentially adsorbed.Specifically, when β＞1, show that sorbent material is to the preferentially adsorbed of C component; When β＜1, show that sorbent material is to the preferentially adsorbed of D component.Consider that from isolating complexity preferably make selectivity β＞2, the β value is high more, fractionation by adsorption is carried out with regard to easy more.Obviously selectivity is good more, and the amount of the sorbent material that production equivalent purpose product is used is just few more.In addition, theoretically, extract component relatively, must be equal to or less than 1 the selectivity of strippant.
Desorption rate be meant sorbent material reach absorption saturated after, under certain strippant effect, to extracting the desorption rate of component.Desorption rate can reduce the strippant consumption faster, improves the throughput of purpose product, reduces the process cost of tripping device.Under the condition that strippant is determined, desorption rate depends on the cation type of sorbent material and the exchange degree in zeolite framework, and is also relevant with the silica alumina ratio of the water content of sorbent material, molecular sieve simultaneously.
Be the absorption of test sorbent material and the characteristic of desorb, use a kind of dynamic test set to measure loading capacity, selectivity and desorption rate.This device is that 45 milliliters helical disk tubular type adsorption column is formed by volume, and spiral pipe is made by the stainless steel tube of 8 * 1 * 1200 millimeters of φ, manages high 18 centimetres.Adsorption column is placed in to have in the temperature controlled vertical electric furnace and heats.End entrance links to each other with nitrogen system with fresh feed pump on the adsorption column, and the lower end outlet connects pressure controlled valve and is connected with the effluent collector.The liquid efflunent gas chromatographic analysis.
Use said apparatus to carry out selectivity and other data that conventional pulse testing is measured absorption system.Pack into the adsorption column concussion of load weighted sorbent material is tamped, and in 180～200 ℃ of activation dehydrations down, the control water-content is not more than 5 and weighs % in the presence of nitrogen.Earlier drain nitrogen, be warming up to 180 ℃, boost to 0.8MPa with strippant toluene or p-Diethylbenzene.Pump into raw material after 10 minutes by liquid hour air speed 1.0, feed strippant with same air speed again, form with the gas chromatographic analysis effluent simultaneously.Strippant contains 70% the normal heptane that is not adsorbed.Contain 5% positive nonane in the raw material as tracer agent, at first go out the peak, it can provide the dead volume of adsorption column.The mid point of tracer agent peak width at half height as zero point, is measured each component peak width at half height mid point to the net retention volume R at zero point, and the partition ratio the when net retention volume of component is with balance arbitrarily is directly proportional, and it has reflected the character of adsorption equilibrium.Net retention volume be selectivity β value than promptly.Chromatogram draws the envelope curve of each component respective peaks, and its peak width at half height W provides the information of each constituent mass transfer rate, and the peak width at half height W of certain component can show with the milliliter numerical table of the strippant that is pumped at interval during this period of time.The peak width at half height of certain component is narrow more, shows that sorbent material is fast more to the speed of the absorption of this component and desorb.
The sorbent material of the inventive method preparation is applicable to the liquid phase adsorption separation process of arene isomer, the arene isomer that particularly separates contraposition from described isomer is as fractionation by adsorption p-Xylol from the mixture of o-Xylol, m-xylene, p-Xylol and ethylbenzene.
Described liquid phase adsorption separation can adopt the multicolumn serial arrangement to operate, and also can adopt the simulation moving-bed of rotary valve to operate.The working pressure of fractionation by adsorption is 0.5～1.0MPa, and temperature is 170～200 ℃.
Further describe the present invention below by example, but the present invention is not limited to this.
Sorbent material strength detection method is to adopt DL-II type granule strength determinator (Dalian Chemical Research ﹠. Design Inst.'s productions) in the example, and at stainless steel cylinder about 1.5 milliliters of sorbent materials of packing into, saturated naturally through air, the sieve that mistake is 297 microns is weighed.Thimble with the stainless steel cylinder shrink-fit is installed during mensuration, after pressing down once, pre-set pressure pours out sorbent material, sieve after 297 microns is weighed, and calculates the percentage of damage of sorbent material under setting pressure according to the reduction of sorbent material, is crushing strength.
The ash content of sorbent material is pressed USP3, and 878,127 method is measured.Sorbent material is at room temperature weighed, put into muffle furnace then, rise to 900 ℃ of roastings 5 hours to constant weight under nitrogen protection, reduce to room temperature, weigh again, both differences are ash oontent.
Example 1
Prepare sorbent material of the present invention.
NaX and kaolin (Linfen, Shanxi product) mixing are made powder.Wherein the NaX relative crystallinity is 101%, and framework si-al ratio is 2.36, and grain-size is 1 micron, and the massfraction of chemical element compositional analysis is as follows:
Na
2O?15％，SiO
2?52％，Al
2O
3?32％，K
2O?0.59％，Fe
2O
30.27％
57 microns of kaolin median sizes, wherein kaolinite content is 80 quality %, halloysite content is 10 quality %.
(1) preparation master batch: above-mentioned NaX and kaolin are made powder by 95: 5 butt quality than mixing, and the bead that is rolled into particle diameter and is 0.180～0.190 millimeter in the bowling machine rolling disk is as master batch, and the amount of deionized water that adds during spin is 5% of a powder quality.
(2) roller forming: the powder of in batches preparing kaolin and NaX.In the rolling disk of above-mentioned placement master batch, put into kaolin content earlier and be 6% powder spin, the powder consumption is 100 times of master batch amount (in butt), the deionized water that rolling limit, limit adds powder 8% carries out the initial stage spin.After the whole balling-up of powder to be added, add kaolin content and be 10% powder in rolling disk and proceed the spin in mid-term, amount of water is 10% of a powder therebetween.After treating that powder uses up, add kaolin content again and be 12% powder in rolling disk and carry out the later stage spin, amount of water is 10% of a powder therebetween.The spin initial stage: mid-term: the later stage, reinforced mass ratio was 1: 1.7: 0.7.Gained bead after the rolling moulding is sieved, sieve out 0.35～0.80 millimeter bead, 8 hours, 540 ℃ roastings of 120 ℃ of dryings 4 hours.
(3) prepare sorbent material: the NaOH that with bead concentration after the roasting is 1.5M carried out alkaline purification in 1 hour 95 ℃ of immersions, and liquid/solid volume was carried out ion-exchange then than 1.6: 1.0, and exchange solution is the Ba (NO of 0.18M
3)
2, give-and-take conditions are: 90 ℃, the volume space velocity of normal pressure, exchange liquid are 12 o'clock-1, and exchange is than 2.0.After the exchange bead was made adsorbent A in 12 hours in 80 ℃ of dryings, its composition and physico-chemical property see Table 1.
Example 2
Method by example 1 prepares adsorbent B, contains 90% kaolinite in the different kaolin that is to use.The composition and the physico-chemical property of adsorbent B see Table 1.
Comparative Examples
Method by example 1 prepares sorbent material, it is 10% powder that different is (2) step is once prepared kaolin content during roller forming, it is positioned over roller forming in the rolling disk, carries out the barium exchange by (3) one step process then and obtain sorbent material C, its composition and physico-chemical property see Table 1.
Example 4～6
Following example is estimated the performance of sorbent material.
Get 45 gram sorbent materials, place the helical disk tubular type adsorption column of the described dynamic checkout unit of specification sheets, concussion is tamped.With toluene is that strippant, nonane are that tracer agent is tested, and the absorption raw material consists of: ethylbenzene 5%, p-Xylol 5%, m-xylene 5%, o-Xylol 5%.The performance measurement of sorbent material the results are shown in Table 2.The loading capacity of sorbent material is represented with C in the table 2, and selectivity represents that with β desorption rate is represented with Wp with the strippant suction volume that reaches in the p-Xylol peak width at half height time.
Table 1
| Project example 1 example 2 Comparative Examples | |
| Sorbent material numbering A B C sorbent material is formed quality % BaX 93.7 92.5 90 kaolin 6.3 7.5 10 | |
| Bright basic bulk density, gram per centimeter 3???????????0.85????????0.84????????0.82 | |
| Crushing strength, % 130 newton 0.9 0.9 1.0 200 newton 2.8 2.9 2.9 250 newton 10.0 9.9 10.1 | |
| Ash content does not have and has | |
| Size-grade distribution | ＜297 micron 1.48 0.78 0.30 297～420 micron 24.38 24.22 25.21 420～590 microns 43.16 44.00 43.11 590～740 microns 20.13 20.04 19.52＞740 microns 10.85 10.96 11.86 |
| Specific surface area, rice 2/ gram 515 514 515 pore volumes, milliliter/gram 0.235 0.236 0.237 skeleton the temperature of subsiding, ℃ 1,021 1,026 1032 | |
Table 2
The following component of subscript letter representative in the table 1: XY-dimethylbenzene, P-p-Xylol, M-m-xylene, O-o-Xylol, E-ethylbenzene
Claims (12)
1, a kind of p-Xylol sorbent material, comprise that massfraction is 88～95% adsorption activity component and 5～12% kaolin, described adsorption activity component is selected from the X zeolite or the Y zeolite of Ba or Ba and K exchange, it is characterized in that the bright basic bulk density of sorbent material is not less than 0.84 gram per centimeter
3
2,, it is characterized in that described active ingredient is BaX or BaKX according to the described sorbent material of claim 1.
3, according to claim 1 or 2 described sorbent materials, it is characterized in that the content of crystallization material in the kaolin is at least 90 quality %, described crystallization material is kaolinite, dickite, nacrite, refractory pebbles or halloysite or their mixture.
4,, it is characterized in that containing in the kaolin halloysite of kaolinite 5～15 quality % of 75～95 quality % according to the described sorbent material of claim 3.
5, according to claim 1 or 2 described sorbent materials, when it is characterized in that described active ingredient is BaKX, the mol ratio of Ba and K is 10～40.
6, according to claim 1 or 2 described sorbent materials, it is characterized in that described sorbent material is a microspheric form, its size distribution is 297～740 microns, the basic bulk density that burns is 0.84～0.90 gram per centimeter
3
7, the described preparation of adsorbent method of a kind of claim 1 comprises the steps:
(1) preparation master batch: with X zeolite or Y zeolite and kaolin mixing, make particle diameter and be 0.180～0.190 millimeter master batch, kaolin content is less than 5 quality % in the master batch;
(2) roller forming: the rolling disk that master batch is placed roller press, prepare X zeolite or Y zeolite and kaolinic powder carries out roller forming in batches, kaolin content is 5～7 quality % in the used powder of spin initial stage, kaolin content is 8～10 quality % in the spin used powder in mid-term, kaolin content is 11～13 quality % in the used powder of spin later stage, the water yield that each phase spin sprays into is 15～20% of a used powder quality, and spin initial stage, mid-term, used powder quality ratio of later stage are 1: 1.5～1.9: 0.5～0.9; The bead of choosing particle diameter and be 0.35～0.80 millimeter carries out drying, 500～700 ℃ of roastings;
(3) preparation sorbent material: the bead after the roasting is carried out the exchange of barium ion exchange or barium and potassium ion after with the alkaline solution dip treating again, exchange after drying.
8, in accordance with the method for claim 7, it is characterized in that containing in the described kaolin halloysite of kaolinite 5～15 quality % of 75～95 quality %.
9, in accordance with the method for claim 7, it is characterized in that described kaolin median size is 57～74 microns.
10, in accordance with the method for claim 7, it is characterized in that described alkaline solution of (3) step is the sodium hydroxide solution of concentration 1.5～4.0 mol, alkali lye is 1.1～2.0: 1 with the liquid/solid volume ratio of bead during processing, and temperature is 90～95 ℃.
11, in accordance with the method for claim 7, it is characterized in that described barium and the potassium ion exchange of (3) step is that soluble salt solution with potassium and barium carries out ion-exchange, or first soluble salt with potassium exchanges, exchange with sylvite again.
12, in accordance with the method for claim 11, the soluble salt that it is characterized in that barium is bariumchloride or nitrate of baryta.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137917 CN1261201C (en) | 2003-05-30 | 2003-05-30 | Paraxylene adsorbent and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137917 CN1261201C (en) | 2003-05-30 | 2003-05-30 | Paraxylene adsorbent and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1552515A true CN1552515A (en) | 2004-12-08 |
| CN1261201C CN1261201C (en) | 2006-06-28 |
Family
ID=34323600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03137917 Expired - Lifetime CN1261201C (en) | 2003-05-30 | 2003-05-30 | Paraxylene adsorbent and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261201C (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009097747A1 (en) * | 2008-01-31 | 2009-08-13 | China Petroleum & Chemical Corporation | Agglomerated zeolite adsorbent and preparation method thereof |
| CN102861551A (en) * | 2011-07-05 | 2013-01-09 | 三星Total株式会社 | Bax type zeolite granule and process for preparing the same |
| RU2491322C2 (en) * | 2008-06-26 | 2013-08-27 | Юоп Ллк | Method of separating p-xylenes from mixture of c8- and c9-aromatic hydrocarbons and device for its realisation |
| CN106423047A (en) * | 2015-08-10 | 2017-02-22 | 中国石油化工股份有限公司 | Spherical n-alkane adsorbent and preparation method thereof |
| CN106552583A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of ethylbenzene adsorbent and preparation method thereof |
| CN106552582A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | From C8The adsorbent and preparation method of ethylbenzene are separated in aromatic hydrocarbons |
| CN108262004A (en) * | 2017-01-03 | 2018-07-10 | 中国石油化工股份有限公司 | Paraxylene adsorbent and preparation method thereof |
| CN108262005A (en) * | 2017-01-03 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of bead adsorbent of adsorption stripping dimethyl benzene and preparation method thereof |
| TWI629098B (en) * | 2013-09-09 | 2018-07-11 | 法商愛克瑪公司 | Zeolitic adsorbents with large external surface area, method of preparation thereof and uses thereof |
| CN108525641A (en) * | 2017-03-01 | 2018-09-14 | 中国石油化工股份有限公司 | The bead adsorbent and preparation method of adsorption stripping dimethyl benzene |
| CN108525650A (en) * | 2017-03-01 | 2018-09-14 | 中国石油化工股份有限公司 | A kind of X/Silicalite-1 core shells molecular sieve and preparation method thereof |
| CN108854945A (en) * | 2006-07-19 | 2018-11-23 | 阿肯马法国公司 | Agglomerated zeolitic absorbents, their production method and their purposes |
| CN109692659A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of binder free spherical shape paraxylene adsorbent and preparation method thereof |
| CN111097372A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of m-xylene adsorbent |
| CN111097371A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of paraxylene adsorbent |
| CN112138628A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Composite layer coalescence type adsorbent and preparation method thereof |
| CN113087585A (en) * | 2020-01-08 | 2021-07-09 | 中国石化工程建设有限公司 | Method for producing paraxylene and ethylbenzene from mixed C8 aromatic hydrocarbons |
-
2003
- 2003-05-30 CN CN 03137917 patent/CN1261201C/en not_active Expired - Lifetime
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854945B (en) * | 2006-07-19 | 2021-01-26 | 阿肯马法国公司 | Agglomerated zeolitic adsorbents, method for their production and their use |
| CN108854945A (en) * | 2006-07-19 | 2018-11-23 | 阿肯马法国公司 | Agglomerated zeolitic absorbents, their production method and their purposes |
| CN101497022B (en) * | 2008-01-31 | 2011-06-15 | 中国石油化工股份有限公司 | Coalescence type zeolite sorbent and preparation method thereof |
| US8791039B2 (en) | 2008-01-31 | 2014-07-29 | China Petroleum & Chemical Corporation | Agglomerated zeolite adsorbents and process for producing the same |
| WO2009097747A1 (en) * | 2008-01-31 | 2009-08-13 | China Petroleum & Chemical Corporation | Agglomerated zeolite adsorbent and preparation method thereof |
| RU2491322C2 (en) * | 2008-06-26 | 2013-08-27 | Юоп Ллк | Method of separating p-xylenes from mixture of c8- and c9-aromatic hydrocarbons and device for its realisation |
| CN102861551A (en) * | 2011-07-05 | 2013-01-09 | 三星Total株式会社 | Bax type zeolite granule and process for preparing the same |
| CN102861551B (en) * | 2011-07-05 | 2015-01-07 | 三星Total株式会社 | Bax type zeolite granule and process for preparing the same |
| TWI629098B (en) * | 2013-09-09 | 2018-07-11 | 法商愛克瑪公司 | Zeolitic adsorbents with large external surface area, method of preparation thereof and uses thereof |
| CN106423047A (en) * | 2015-08-10 | 2017-02-22 | 中国石油化工股份有限公司 | Spherical n-alkane adsorbent and preparation method thereof |
| CN106423047B (en) * | 2015-08-10 | 2019-12-27 | 中国石油化工股份有限公司 | Spherical normal alkane adsorbent and preparation method thereof |
| CN106552582B (en) * | 2015-09-29 | 2019-05-17 | 中国石油化工股份有限公司 | From C8The adsorbent and preparation method of ethylbenzene are separated in aromatic hydrocarbons |
| CN106552583B (en) * | 2015-09-29 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of ethylbenzene adsorbent and preparation method thereof |
| CN106552583A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of ethylbenzene adsorbent and preparation method thereof |
| CN106552582A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | From C8The adsorbent and preparation method of ethylbenzene are separated in aromatic hydrocarbons |
| CN108262004B (en) * | 2017-01-03 | 2020-11-13 | 中国石油化工股份有限公司 | Paraxylene adsorbent and preparation method thereof |
| CN108262005A (en) * | 2017-01-03 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of bead adsorbent of adsorption stripping dimethyl benzene and preparation method thereof |
| CN108262004A (en) * | 2017-01-03 | 2018-07-10 | 中国石油化工股份有限公司 | Paraxylene adsorbent and preparation method thereof |
| CN108262005B (en) * | 2017-01-03 | 2020-11-13 | 中国石油化工股份有限公司 | Small ball adsorbent for adsorbing and separating p-xylene and preparation method thereof |
| CN108525650A (en) * | 2017-03-01 | 2018-09-14 | 中国石油化工股份有限公司 | A kind of X/Silicalite-1 core shells molecular sieve and preparation method thereof |
| CN108525641A (en) * | 2017-03-01 | 2018-09-14 | 中国石油化工股份有限公司 | The bead adsorbent and preparation method of adsorption stripping dimethyl benzene |
| CN108525641B (en) * | 2017-03-01 | 2020-11-13 | 中国石油化工股份有限公司 | Small ball adsorbent for adsorbing and separating p-xylene and preparation method thereof |
| CN109692659A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of binder free spherical shape paraxylene adsorbent and preparation method thereof |
| CN109692659B (en) * | 2017-10-24 | 2022-11-15 | 中国石油化工股份有限公司 | Binder-free spherical paraxylene adsorbent and preparation method thereof |
| CN111097372B (en) * | 2018-10-29 | 2022-03-11 | 中国石油化工股份有限公司 | Preparation method of m-xylene adsorbent |
| CN111097371B (en) * | 2018-10-29 | 2022-03-11 | 中国石油化工股份有限公司 | Preparation method of paraxylene adsorbent |
| CN111097371A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of paraxylene adsorbent |
| CN111097372A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of m-xylene adsorbent |
| CN112138628A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Composite layer coalescence type adsorbent and preparation method thereof |
| CN112138628B (en) * | 2019-06-26 | 2023-04-07 | 中国石油化工股份有限公司 | Composite layer coalescence type adsorbent and preparation method thereof |
| CN113087585A (en) * | 2020-01-08 | 2021-07-09 | 中国石化工程建设有限公司 | Method for producing paraxylene and ethylbenzene from mixed C8 aromatic hydrocarbons |
| CN113087585B (en) * | 2020-01-08 | 2023-01-06 | 中国石化工程建设有限公司 | Method for producing paraxylene and ethylbenzene from mixed C8 aromatic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1261201C (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1261201C (en) | Paraxylene adsorbent and preparing method thereof | |
| CN1267185C (en) | Paraxylene sorbent and its preparing method | |
| CN1191118C (en) | Adsorbent for adsorption stripping dimethyl benzene and its preparing process | |
| TWI641419B (en) | Zeolitic adsorbents, their process of preparation and their uses | |
| KR101227756B1 (en) | Agglomerated zeolitic adsorbents, method of preparaing them and uses thereof | |
| JP5324441B2 (en) | Agglomerated zeolite adsorbents, processes for their production and their use | |
| US8791039B2 (en) | Agglomerated zeolite adsorbents and process for producing the same | |
| JP6437557B2 (en) | Zeolite adsorbent having a large external surface area, method for producing the same and use thereof | |
| KR20130115338A (en) | Binderless zeolitic adsorbents, methods for producing binderless zeolitic adsorbents, and adsorptive separation processes using the binderless zeolitic adsorbents | |
| CN102167652B (en) | Adsorbent for adsorbing and separating m-xylene and preparation method of same | |
| CN105339082A (en) | Zeolite adsorbents comprising EMT zeolite, method for preparing same and uses thereof | |
| CN103429532A (en) | Aluminosilicate X-type zeolite compositions with low LTA-type zeolite | |
| CN111097372B (en) | Preparation method of m-xylene adsorbent | |
| CN101745364B (en) | Adsorbent for adsorption separation of m-Xylene and preparation method thereof | |
| CN108262005B (en) | Small ball adsorbent for adsorbing and separating p-xylene and preparation method thereof | |
| CN108262004B (en) | Paraxylene adsorbent and preparation method thereof | |
| CN110508240A (en) | A kind of preparation method of coalescence type adsorbent | |
| CN106552582A (en) | From C8The adsorbent and preparation method of ethylbenzene are separated in aromatic hydrocarbons | |
| CN1339334A (en) | Preparing method for adsorbeng for selectively adsorbing and separating aromatic isomer | |
| CN108525643A (en) | A kind of paraxylene adsorbent and preparation method thereof | |
| CN108525641B (en) | Small ball adsorbent for adsorbing and separating p-xylene and preparation method thereof | |
| CN115990456B (en) | Para-xylene adsorbent and preparation method and application thereof | |
| CN103517876A (en) | Binder-converted aluminosilicate X-type zeolite compositions with low LTA-type zeolite | |
| CN111097371B (en) | Preparation method of paraxylene adsorbent | |
| CN114425297B (en) | Para-disubstituted benzene adsorbent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060628 |