CN1142024C - Molecular sieve RE ion exchange method - Google Patents
Molecular sieve RE ion exchange method Download PDFInfo
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- CN1142024C CN1142024C CNB011342765A CN01134276A CN1142024C CN 1142024 C CN1142024 C CN 1142024C CN B011342765 A CNB011342765 A CN B011342765A CN 01134276 A CN01134276 A CN 01134276A CN 1142024 C CN1142024 C CN 1142024C
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Abstract
The present invention relates to an exchange method of rare earth (RE) ions of a molecular sieve. The method comprises the following steps: a molecular sieve and water are pulped together, and obtained serous fluid is continuously conveyed to the filtration fabric of a horizontal vacuum belt filter; then, the filtration fabric is sequentially passes through a filter cake forming region and an ion exchange region, a liquid receiver under the filtration fabric of the filter cake forming region and the ion exchange region is vacuumized, and a filter cake is washed, sucked dry and detached from the filtration fabric, wherein the molecular sieve is a Y-shaped molecular sieve of once exchange and once baking; acid and/or salt is also added to the serous fluid, and the dosage of the acid and/or the salt is 0.1 to 5 wt % of the dosage of the molecular sieve. The vacuum degree of the liquid receiver under the filtration fabric of the filter cake forming region ensures that no crack is formed on the surface of the filter cake. A solution containing RE ions is added to the upper part of the filter cake in the ion exchange region, the dosage of the solution containing the RE ions enables the weight ratio of an RE oxide to the molecular sieve is 0.01 to 0.5.
Description
Invention field
The invention relates to a kind of ion-exchange techniques of molecular sieve, more specifically say so about a kind of RE ion exchange method of molecular sieve.
Background technology
Y zeolite is the active ingredient commonly used of catalyzer, in the catalyzer, prepares by the NaY molecular sieve as Y zeolite contained in the hydrocarbon cracking catalyzer.Sodium Y molecular sieve and the aqueous solution that contains ammonium ion and/or rare earth ion are carried out ion-exchange, washing, Y zeolite dry and that roasting obtains to be commonly referred to one and to hand over a roasting Y zeolite.It comprises that one hands over a roasting super-stable Y molecular sieves USY, to hand over a roasting rare earth Y type molecular sieve REY, to hand over a roasting rare earth hydrogen Y zeolite REHY and to hand over a roasting hydrogen Y molecular sieve HY.The lattice constant of one friendship, one roasting Y zeolite is the 24.48-24.66 dust, and sodium oxide content is the heavy % of 3-5.One hands over the sodium content in the roasting Y zeolite still higher, can not still need to carry out ion-exchange to reduce sodium content wherein and/or to introduce rare earth ion or other ions directly as the active ingredient of cracking catalyst.
At present, industrial employing is introduced rare earth ion with the method that Y zeolite carries out rare earth ion exchanged, and the method for carrying out rare earth ion exchanged has two kinds.
First method is with Y zeolite and the aqueous solution making beating that contains rare earth ion, carries out ion-exchange, filtration, washing, drying, roasting or not roasting.Wherein, filter the employing flame filter press.The shortcoming that adopts this method is that efficient is low, and the water consumption is big.
Second method is that Y zeolite is mixed the water slurry that making beating forms a kind of Y zeolite with water, this slurry directly is loaded on the filter cloth of band filter, on filter cloth, form certain thickness filter cake, the aqueous solution that adds rare earth ion then from the filter cake top, under filter cloth in the liquid receiver under the vacuum action, ion-exchange takes place continuously by filter cake the time in the solution that contains rare earth ion.The advantage of using band filter is can integrate solid-liquid separation, washing, exchange and filter, the efficient height, and the water consumption is little.
US 3,943,233 disclose the method for a large amount of trickle solid particles of a kind of continuous processing, this method comprises that the slurries with a kind of fine solid particle are supplied to a mobile continuous horizontal band filter, this band filter is equipped with a vacuum chamber with part separated from each other, wherein, each part separated from each other with one independently the liquid susceptor link to each other with vacuum controller.On the transition band slurries, impose enough vacuum, obtain containing in a kind of particulate space the filter cake thin layer of the lubricous dry of water, when filter cake passes through described vacuum chamber continuously, it can be contacted with the solution of described particle generation mass trnsfer reaction with a kind of, simultaneously, vacuum degree control can be formed an immobilized liquid Xiao Chi on filter cake, after from filter cake, flowing down enough liquid, form a kind of smoothly, the surface does not have be full of cracks, contains the filter cake of liquid between the filter cake particle, on filter cake, add another kind of liquid, and control enough vacuum tightness, and make liquid flow through filter cake fast, unload filter cake from strainer.
US 3,943, but 233 also disclose a kind of method of carrying out ion-exchange continuously of fluidization zeolite granular, this method comprises described zeolite granular and first kind of liquid making beating, these slurries are loaded into the infeed end of a continuous horizontal belt vacuum filter with the speed of substantially constant, move the transition band that slurry is housed continuously, order forms the district by a filter cake, at least one ion-exchange area and a washing section, simultaneously independently impose vacuum on the liquid receiver under the transition band, unload filter cake from transition band at each.The method is characterized in that filter cake does not have check surface basically when leaving filter cake formation district, but can contain liquid between the space of fluidised zeolite granular, in the ion exchange treatment process, filter cake is at ion-exchange area, under filtration condition, contact with a kind of ion-exchange liquids, mode with a kind of filter cake is left ion-exchange area, this filter cake is smooth, basically there is not check surface, and can contain liquid between the space of fluidised zeolite granular, and under vacuum, wash the filter cake after the ion-exchange fast.
Experiment shows that US 3,943,233 described methods are applicable to ion-exchange, the washing process of some big solid particulates and part molecular sieve.But, because one hands in the aqueous slurry of a roasting Y zeolite, the very tiny and reason of handing over roasting Y zeolite self inherent nature of the particle of molecular sieve, after slurries of handing over a roasting Y zeolite to mix making beating formation with water are loaded the transition band of going up band filter, formed filter cake is a kind of very filter cake of densification, water-permeable extreme difference, filtration velocity (liquid sees through the speed of filter cake) is quite slow, and the rare earth ion exchanged process can't be carried out.Therefore, still on band filter, do not hand over a roasting Y zeolite to carry out the method for rare earth ion exchanged in the prior art to one.
Summary of the invention
The purpose of this invention is to provide a kind of new not only water-saving efficient but also high molecular sieve switching method.
Molecular sieve RE ion exchange method provided by the invention comprises pulls an oar a kind of molecular sieve with water, the slurries that obtain are loaded on the filter cloth of horizontal belt filter continuously, order forms district and an ion-exchange area by a filter cake, impose vacuum in the liquid receiver below the filter cloth of filter cake formation district and ion-exchange area, washing, blot filter cake, unload filter cake from filter cloth, wherein, described molecular sieve is a friendship one a roasting Y zeolite, acid and/or salt have also been added in the described slurries, the consumption of described acid and/or salt is the heavy % of the 0.1-5 of molecular sieve consumption, the vacuum tightness that described filter cake forms in district's liquid receiver guarantees not have be full of cracks substantially on the filter cake surface, at described ion-exchange area, add the solution that contains rare earth ion on the top of filter cake, it is 0.01-0.5 that the consumption that contains rare-earth ion solution makes the weight ratio of rare earth oxide and molecular sieve.
Compared with prior art, method provided by the invention has overcome prior art and can not hand over a roasting Y zeolite to carry out the shortcoming of rare earth ion exchanged to one on band filter, has successfully finished on band filter and has handed over a roasting Y zeolite to carry out rare earth ion exchanged to one.Method provided by the invention has the advantage of using band filter to exchange certainly, and promptly the water consumption is little, the advantage that efficient is high.
Embodiment
According to method provided by the invention, described one hands over a roasting Y zeolite to comprise that one hands over a roasting ultra-steady Y molecular sieve USY, one hands over a roasting rare-earth Y molecular sieve REY, to hand over a roasting rare earth hydrogen Y molecular sieve REHY and to hand over a roasting hydrogen Y molecular sieve HY, and these molecular sieves and preparation method thereof are conventionally known to one of skill in the art.Handing over a roasting hydrogen Y molecular sieve with one is example, and its preparation method is normally with the sodium Y molecular sieve and the aqueous solution that contains ammonium ion, as ammonium chloride, ammonium sulfate solution mixing carrying out ion-exchange, washing, dry and roasting.Wherein, contain the concentration of the aqueous solution of ammonium ion and consumption and give-and-take conditions also for conventionally known to one of skill in the art, as in ammonium salt, the concentration of the ammonium ion aqueous solution is generally the 50-300 grams per liter, be preferably the 100-200 grams per liter, the temperature of exchange is a room temperature to 100 ℃, is preferably 50-90 ℃, the time of exchange is 0.5-2 hour, is preferably 0.5-1 hour.Condition dry and roasting is conventionally known to one of skill in the art, is room temperature to 200 ℃ as the exsiccant temperature, is preferably 100-150 ℃, and maturing temperature is 500-800 ℃, is preferably 600-700 ℃, and roasting time is 1-3 hour, is preferably 2-3 hour.One hands over a roasting Y zeolite to have following common character: lattice constant is the 24.48-24.66 dust, and sodium oxide content is the heavy % of 3-5.
Described one hands over a roasting Y zeolite also to be available commercially by existing method preparation.
Described acid is selected from one or more in water-soluble acid, comprise in water-soluble mineral acid and the organic acid one or more, example hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetate, propionic acid, phenylformic acid etc. wherein, are preferably hydrochloric acid, sulfuric acid, nitric acid and/or phosphoric acid.
Described salt refers to one or more in water-soluble various salt, as in the soluble salt hydrochlorate of ammonium, basic metal, aluminium, iron, rare earth, vitriol, nitrate, the phosphoric acid salt one or more, wherein, be preferably in hydrochloride, vitriol and the nitrate of basic metal, ammonium, iron, rare earth one or more, as in the muriate of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, sodium sulfate, sodium-chlor, SODIUMNITRATE and rare earth one or more.
The consumption of described acid and/or salt is the heavy % of the 0.1-5 of molecular sieve consumption, is preferably the heavy % of 0.5-3.
In the slurries that described molecular sieve and water making beating obtain, the content range of molecular sieve is conventionally known to one of skill in the art, and the content of molecular sieve is generally the 100-300 grams per liter in the described slurries.The temperature of described slurries can be 5-100 ℃, is preferably 50-90 ℃.
According to method provided by the invention, can be by flow implementation the present invention shown in Figure 1.
One, the formation of filter cake
With 5-100 ℃, preferred 50-90 ℃ the molecular sieve pulp that contains acid and/or salt is loaded on the filter cloth 3 of horizontal vacuum band-type filter machine through pipeline 2 continuously from making beating jar 1, filter cloth moves continuously, enter filter cake and form district 4, the liquid receiver 5 in filter cake formation district 4 is positioned at the below of filter cloth 3, liquid receiver 5 is vacuumized, under vacuum action, liquid in filter cloth 3 spreading masses enters in the liquid receiver 5 by filter cloth 3, and the waste liquid in the liquid receiver 5 is by pipeline 6 dischargings.Slurry on filter cloth 3 forms filter cake simultaneously, and the filter cake thickness that the loading speed of slurries should guarantee to form is preferably 0.8-1.5 centimetre at 0.5-2.0 centimetre.Vacuum tightness in the vacuum chamber 5 makes the filter cake surface not have be full of cracks substantially.Vacuum tightness in the vacuum chamber 5 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.The exchange waste liquid that wherein said acid and/or salt can be got by the ion-exchange area 7 of the following stated provides, promptly additionally do not add acid and/or salt, directly hand over a roasting Y zeolite and water to mix making beating, make the described slurry that contains molecular sieve with the exchange waste liquid in the liquid receiver 8 of ion-exchange area 7 and.This has reduced the consumption of acid and/or salt and the consumption of water on the one hand, has also reduced the sewage emissions amount.
Two, rare earth ion exchanged
With moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters ion-exchange area 7, the liquid receiver 8 of ion-exchange area 7 is positioned at the below of filter cloth 3, liquid receiver 8 is vacuumized, and above filter cake, adding temperature by container 9 by pipeline 10 is 5-100 ℃, preferred 20-90 ℃ the aqueous solution that contains rare earth ion.Under vacuum action, the aqueous solution that contains rare earth ion has also carried out ion-exchange by filter cake the time.
Vacuum tightness in the liquid susceptor 8 will make the filter cake surface keep the moistening be full of cracks that do not occur.Vacuum tightness in the liquid susceptor 8 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The consumption and the concentration that contain the aqueous solution of rare earth ion are decided according to measuring on the final Y zeolite middle-weight rare earths oxide compound.In general, it is 0.01-0.5 that the consumption that contains the aqueous solution of rare earth ion makes the weight ratio of rare earth oxide and molecular sieve, is preferably 0.05-0.2, in oxide compound, the aqueous solution middle-weight rare earths ion content that contains rare earth ion is the 10-100 grams per liter, is preferably the 20-80 grams per liter.The temperature that contains the aqueous solution of rare earth ion can be 5-100 ℃, is preferably 20-90 ℃.Described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, the neptunium, is preferably lanthanum, cerium, lanthanum rich mischmetal or cerium-rich mischmetal.The precursor of rare earth ion is selected from rare earth solubility salt, as rare earth chloride, rare earth nitrate etc.
Exchange waste liquid in the liquid receiver 8 is by pipeline 11 dischargings, described exchange waste liquid except be used for molecular sieve making beating, can also mix with the higher fresh exchange liquid of concentration, perhaps directly dissolve rare earth compound and make exchange liquid, the promptly described aqueous solution that contains rare earth ion.
Three, washing
Washing methods is conventionally known to one of skill in the art, on the filter cake that ion-exchange area 7 obtains, adds deionized water from container 12 through pipeline 13, simultaneously, liquid receiver 14 is vacuumized, under vacuum action, liquid sees through filter cake, with the survivor ion in the filter cake, and negatively charged ion flush away particularly.The weight ratio of deionized water and molecular sieve is generally 1-15, is preferably 2-10, and the temperature of deionized water is 5-100 ℃, is preferably 20-90 ℃.
The waste liquid that liquid receiver 14 is collected is discharged through pipeline 15, can be used to the higher fresh exchange liquid of compound concentration, also can be used to mix with fresh exchange liquid, is used as exchange liquid then.Vacuum tightness in the liquid receiver 14 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Four, blot
The method that blots is conventionally known to one of skill in the art.Under the vacuum action, the liquid in the filter cake is by further sucking-off in the liquid receiver 16 of filter cake after the washing under filter cloth 3.Liquid in the liquid receiver 16 is discharged through pipeline 17, and the liquid phase in its purposes and the receptor 14 together.Vacuum tightness in the liquid receiver 16 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Five, unload the filter cake that blots at last.
The following examples will the present invention is described further.
Comparative Examples 1
The switching method of the existing rare earth ion of this Comparative Examples explanation.
With a friendship one roasting ultra-steady Y molecular sieve (lattice constant is 24.56 dusts, and sodium oxide content is 4.3 heavy %, and Qilu Petrochemical company catalyst plant is produced), and re chloride (contain rare earth oxide 100 grams per liters, wherein, La
2O
3Content is 33.2 grams per liters, CeO
2Content is 59.1 grams per liters, other rare earth oxide content 8 grams per liters) solution presses molecular sieve: RE
2O
3: H
2O=1: 0.12: 10 weight ratio is mixed making beating, is warming up to 90 ℃, under agitation carries out ion-exchange 60 minutes, filters then, and the filtrate A1 that obtains is standby, and the content of rare earth chloride is about 4.5 grams per liters among the filtrate A1, and the content of sodium-chlor is about 6 grams per liters.With temperature is 90 ℃ of 10 times of filter cakes that obtain to the deionized water wash of molecular sieve weight, then at 120 ℃ of oven dry filter cakes, obtains containing the super-stable Y molecular sieves B1 of rare earth.B1 middle-weight rare earths oxide compound RE
2O
3Content is 5.0 heavy %, wherein La
2O
3Content be 1.64 heavy %, CeO
2Content be 2.96 heavy %, the content of other rare earth oxide is 0.4 heavy %, sodium oxide content is 1.3 heavy %.Wherein in the molecular sieve oxide content measuring method referring to petrochemical complex analytical procedure (RIPP test method), p368-370, Science Press, 1990.Sodium oxide adopts aas determination.The content of rare earth chloride and sodium-chlor is got by calculating among the filtrate A1.
Comparative Examples 2
The existing RE ion exchange method of this Comparative Examples explanation.
Method by Comparative Examples 1 is carried out ion-exchange, filtration, washing and drying, different is that (lattice constant is 24.65 dusts with a friendship one roasting hydrogen Y molecular sieve, sodium oxide content is 4.5 heavy %, and Qilu Petrochemical company catalyst plant is produced), obtain the standby and Y zeolite B2 of filtrate A2.Rare earth chloride content is about 4 grams per liters among the filtrate A2, and sodium chloride content is about 7 grams per liters.B2 middle-weight rare earths oxide compound RE
2O
3Content is 5.8 heavy %, wherein La
2O
3Content be 1.92 heavy %, CeO
2Content be 3.43 heavy %, the content of other rare earth oxide is 0.5 heavy %, sodium oxide content is 1.3 heavy %.
Comparative Examples 3
The existing RE ion exchange method of this Comparative Examples explanation.
Method by Comparative Examples 1 is carried out rare earth ion exchanged, filtration, washing and drying, and different is that used molecular sieve is that (lattice constant is 24.64 dusts to a friendship one roasting rare-earth Y molecular sieve, rare earth oxide RE
2O
3Content is 14.0 heavy %, wherein La
2O
3Content be 4.7 heavy %, CeO
2Content be 8.3 heavy %, the content of other rare earth oxide is 1.0 heavy %, sodium oxide content is 4.3 heavy %, Qilu Petrochemical company catalyst plant is produced), obtain filtrate A3 and rare earth Y type molecular sieve B3.Rare earth chloride content is about 4 grams per liters among the filtrate A3, and sodium chloride content is about 7 grams per liters.B3 middle-weight rare earths oxide compound RE
2O
3Content is 21.0 heavy %, wherein La
2O
3Content be 7.0 heavy %, CeO
2Content be 12.4 heavy %, other rare earth oxide content is 1.6 heavy %, sodium oxide content is 1.0 heavy %.
Following example adopts cloth formula funnel filtration unit to experimentize, and is used for illustrating method provided by the invention.Owing to adopt cloth formula funnel filtration unit also to experience filter cake formation, ion-exchange, the stage such as wash and blot, just these steps are separately carried out, thus with band filter on the process of carrying out continuously be of equal value.
Example 1
Hand over a roasting ultra-steady Y molecular sieve, deionized water and Comparative Examples 1 described filtrate A1 to mix making beating Comparative Examples 1 described, making molecular sieve content is the slurries that contain molecular sieve of 120 grams per liters, and wherein the consumption of salt (being rare earth chloride and sodium-chlor contained among the used filtrate A1) is 1.1 heavy % of molecular sieve.The molecular sieve pulp that obtains is heated to 90 ℃, pours in the B, simultaneously filter flask is evacuated to 0.07 MPa, formation thickness is 10 millimeters filter cake on filter cloth.When the absence of liquid of filter cake surface, adding rare earth oxide content immediately is 50 grams per liters, and temperature is 90 ℃ re chloride (La wherein
2O
3Content be 16.6 grams per liters, CeO
2Content be 29.6 grams per liters, other rare earth oxide content is 3.8 grams per liters), adding speed guarantees that the filter cake surface does not form be full of cracks, it is 0.1 that the consumption of re chloride makes the weight ratio of rare earth oxide and molecular sieve.When the absence of liquid of filter cake surface, add temperature immediately and be 90 ℃ deionized water wash filter cake, the weight ratio of deionized water and molecular sieve is 3.Take off filter cake then 120 ℃ of oven dry, obtain containing rare earth superstable Y-type molecular sieve Z1.Z1 middle-weight rare earths oxide compound RE
2O
3Content is 5.6 heavy %, wherein La
2O
3Content be 1.9 heavy %, CeO
2The heavy % of content 3.3, the content of other rare earth oxide is 0.4 heavy %, the content of sodium oxide is 0.9 heavy %.
Example 2
Hand over a roasting hydrogen Y molecular sieve, deionized water and Comparative Examples 2 described filtrate A2 to mix making beating Comparative Examples 2 described, make the slurry that molecular sieve content is 200 grams per liters, wherein the consumption of salt (being rare earth chloride and sodium-chlor contained among the used filtrate A2) is 1.7 heavy % of molecular sieve.The molecular sieve pulp that obtains is heated to 90 ℃, pours in the B, simultaneously filter flask is evacuated to 0.05 MPa.Formation thickness is 12 millimeters filter cake on filter cloth.When the absence of liquid of filter cake surface, adding rare earth oxide content immediately is 40 grams per liters, temperature is 90 ℃ a re chloride (ratio of each rare earth oxide is with example 1), adding speed guarantees that the filter cake surface does not form be full of cracks, and it is 0.08 that the consumption of re chloride makes the weight ratio of rare earth oxide and molecular sieve.When the absence of liquid of filter cake surface, add temperature immediately and be 90 ℃ deionized water wash filter cake, the weight ratio of deionized water and molecular sieve is 5.Take off filter cake then 120 ℃ of oven dry, obtain containing rare earth superstable Y-type molecular sieve Z2.Z2 middle-weight rare earths oxide compound RE
2O
3Content be 7.1 heavy %, wherein La
2O
3Content be 2.4 heavy %, CeO
2Content be 4.2 heavy %, the content of other rare earth oxide is 0.5 heavy %, the content of sodium oxide is 0.9 heavy %.
Example 3
Taking by weighing Comparative Examples 3 described hands over a roasting rare-earth Y molecular sieve, deionized water and Comparative Examples 3 described filtrate A3 to mix making beating, making molecular sieve content is the slurry that contains molecular sieve of 150 grams per liters, and wherein the consumption of salt (being rare earth chloride and sodium-chlor contained among the used filtrate A3) is 2.5 heavy % of molecular sieve.The molecular sieve pulp that obtains is heated to 70 ℃, pours in the B, simultaneously filter flask is evacuated to 0.05 MPa.Formation thickness is 8 millimeters filter cake on filter cloth.When the absence of liquid of filter cake surface, adding rare earth oxide content immediately is 50 grams per liters, and temperature is 70 ℃ re chloride (La wherein
2O
3Content be 41.7 grams per liters, CeO
2Content be 3.7 grams per liters, the content of other rare earth oxide is 4.6 grams per liters), adding speed guarantees that the filter cake surface does not form be full of cracks, it is 0.1 that the consumption of re chloride makes the weight ratio of rare earth oxide and molecular sieve.When the absence of liquid of filter cake surface, add temperature immediately and be 70 ℃ deionized water wash filter cake, the weight ratio of deionized water and molecular sieve is 4.Take off filter cake then,, obtain containing rare earth superstable Y-type molecular sieve Z3 120 ℃ of oven dry.Z3 middle-weight rare earths oxide compound RE
2O
3Content be 22.0%, La wherein
2O
3Content be 18.3 heavy %, CeO
2Content be 1.6 heavy %, the content of other rare earth oxide is 2.1 heavy %, the content of sodium oxide is 0.8 heavy %.
Example 4
This example illustrates the applicable cases of method provided by the invention on the full scale plant band filter.
By flow process shown in Figure 1, Comparative Examples 1 described is handed over a roasting super-stable Y molecular sieves, hydrochloric acid and deionized water mix making beating in making beating jar 1, obtain containing the molecular sieve slurry of molecular sieve 150 grams per liters, and the consumption of hydrochloric acid is 1.0 heavy % of molecular sieve consumption.When the exchange waste liquid amount that produces in the liquid receiver 8 was enough, with exchange waste liquid wholly replace hydrochloric acid, it was 1.5 heavy % of molecular sieve consumption that the consumption of waste liquid makes the amount of salt contained in the waste liquid.The slurries that obtain are heated to 80 ℃, be loaded into continuously on the filter cloth 3 of a horizontal vacuum band-type filter machine by pipeline 2 then, filter cloth 3 moves continuously, along with moving of filter cloth, slurry enters the filter cake that is connected with liquid receiver 5 and forms district 4, and the vacuum tightness in the liquid receiver 5 is 0.05 MPa.Form by filter cake that to have formed thickness on district's 4 back filter clothes be 10 millimeters filter cake, the filter cake surface does not have be full of cracks, and waste liquid is collected in liquid receiver 5, and discharges by pipeline 6.
Along with moving of filter cloth, filter cake enters the ion-exchange area 7 that liquid receiver 8 is housed, and the vacuum tightness in the liquid receiver 8 is 0.04 MPa.By the flow of pipeline 10 with 3 cubic metres/hour, adding temperature is 60 ℃ from the container 9 on filter cake top, and rare earth oxide content is the re chloride of 50 grams per liters (ratio of each rare earth oxide is with Comparative Examples 1).It is 0.04 that the consumption of described re chloride makes the weight ratio of rare earth oxide and molecular sieve.Exchange waste liquid in the liquid receiver 8 is used for joining making beating jar 1, as the source of described acid and/or salt.
Along with moving of filter cloth, the exchange fluid exchange is the mixtures of liquids that obtains of the scrub raffinate that obtains of following liquid receiver 14 and liquid receiver 16 and the mixed solution of fresh re chloride, this mixed solution contain equally 50 grams per liters rare earth oxide, it is 0.05 that the consumption of mixed solution makes the weight ratio of rare earth oxide and molecular sieve.
Along with moving of filter cloth, filter cake leaves ion-exchange area 7.Adding temperature from the container 12 on filter cake top by pipeline 13 is 60 ℃ deionized water, and under the vacuum action, liquid is through filter cake liquid receiver 14 in, and the ion that flush away is residual, the consumption of deionized water are 3 times of molecular sieve.Vacuum tightness in the liquid receiver 14 is 0.05 MPa.Scrub raffinate in the liquid receiver 14 is discharged from pipeline 15, and with liquid mixing from liquid receiver 16, be used for and the fresh re chloride exchange liquid that to be mixed with into above-mentioned rare earth oxide content be 50 grams per liters.
After washing finished, filter cake continued to move ahead under the drive of filter cloth, and under the vacuum action in liquid receiver 16, the liquid in the filter cake is by further sucking-off, and the vacuum tightness of liquid receiver 16 is 0.04 MPa.At the filter cloth turning, filter cake and filter cloth are peeled off.Dry filter cakes for 120 ℃, obtain containing the Y zeolite Z4 of rare earth.The content of sodium oxide is 0.9 heavy % among the Z4, and the content of rare earth oxide is 6.0 heavy %.Wherein, La
2O
3Content be 2.0 heavy %, CeO
2Content be 3.5 heavy %, the content of other rare earth oxide is 0.5 heavy %.
Liquid in the liquid receiver 16 is discharged from pipeline 17, mixes with the scrub raffinate that obtains in the liquid receiver 14.
Claims (15)
1. the RE ion exchange method of a molecular sieve, this method comprises pulls an oar a kind of molecular sieve with water, the slurries that obtain are loaded on the filter cloth of horizontal belt filter continuously, order forms district and an ion-exchange area by a filter cake, impose vacuum in the liquid receiver below the filter cloth of filter cake formation district and ion-exchange area, washing, blot filter cake, unload filter cake from filter cloth, it is characterized in that, described molecular sieve is a friendship one a roasting Y zeolite, acid and/or salt have also been added in the described slurries, the consumption of described acid and/or salt is the heavy % of the 0.1-5 of molecular sieve consumption, the vacuum tightness that described filter cake forms in district's liquid receiver guarantees not have be full of cracks substantially on the filter cake surface, at described ion-exchange area, add the solution that contains rare earth ion on the top of filter cake, it is 0.01-0.5 that the consumption that contains rare-earth ion solution makes the weight ratio of rare earth oxide and molecular sieve.
2. method according to claim 1 is characterized in that, described one hands over a roasting Y zeolite to comprise that one hands over a roasting ultra-steady Y molecular sieve, to hand over a roasting rare-earth Y molecular sieve, to hand over a roasting rare earth hydrogen Y molecular sieve and to hand over a roasting hydrogen Y molecular sieve.
3. method according to claim 1 is characterized in that described acid is selected from one or more in water-soluble organic acid and the mineral acid.
4. method according to claim 3 is characterized in that described acid refers to hydrochloric acid, sulfuric acid, nitric acid and/or phosphoric acid.
5. method according to claim 1 is characterized in that described salt refers to one or more in water-soluble salt.
6. according to the said method of claim 5, it is characterized in that described salt is selected from one or more in the soluble salt hydrochlorate, vitriol, phosphoric acid salt, nitrate of ammonium, basic metal, alkaline-earth metal, aluminium, iron, rare earth.
7. method according to claim 6 is characterized in that described salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, sodium sulfate, sodium-chlor, SODIUMNITRATE and the rare earth chloride.
8. method according to claim 1 is characterized in that, described acid and/or salt derive from the exchange waste liquid of ion-exchange area.
9. method according to claim 1 is characterized in that, the consumption of described acid and/or salt is the heavy % of the 0.5-3 of molecular sieve consumption.
10. method according to claim 1 is characterized in that, described slurries are 20-90 ℃ with the temperature that contains rare-earth ion solution.
11., it is characterized in that the content of molecular sieve is the 100-300 grams per liter in the described slurries according to the described method of claim 1.
12. method according to claim 1 is characterized in that, the vacuum tightness that described filter cake forms in district's liquid receiver is the 0.01-0.08 MPa, and the vacuum tightness in the ion-exchange area liquid receiver is the 0.01-0.08 MPa.
13. method according to claim 1 is characterized in that, it is 0.05-0.2 that the described consumption that contains the solution of rare earth ion makes the weight ratio of rare earth oxide and molecular sieve,
14. method according to claim 1 is characterized in that, in oxide compound, the content of rare earth in the described solution that contains rare earth ion is the 10-100 grams per liter.
15. method according to claim 14 is characterized in that, the described solution middle-weight rare earths content that contains rare earth ion is the 20-80 grams per liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011342765A CN1142024C (en) | 2001-10-30 | 2001-10-30 | Molecular sieve RE ion exchange method |
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| CNB011342765A CN1142024C (en) | 2001-10-30 | 2001-10-30 | Molecular sieve RE ion exchange method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102849754A (en) * | 2012-09-28 | 2013-01-02 | 上海恒业化工有限公司 | Ion exchange production method of molecular sieve |
| CN103771444B (en) * | 2012-10-19 | 2016-03-23 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN103771448B (en) * | 2012-10-19 | 2016-01-20 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN103771446B (en) * | 2012-10-19 | 2016-03-23 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN103771441B (en) * | 2012-10-19 | 2015-11-25 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN103771443B (en) * | 2012-10-19 | 2016-03-23 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN103771442B (en) * | 2012-10-19 | 2015-11-25 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN103771445B (en) * | 2012-10-19 | 2016-03-23 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN114031093A (en) * | 2021-11-18 | 2022-02-11 | 江苏国瓷新材料科技股份有限公司 | Method for efficiently preparing oxygen-producing molecular sieve |
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