CN1208134C - Ammonium and rare earth ion mixed exchange method of molecular sieve - Google Patents
Ammonium and rare earth ion mixed exchange method of molecular sieve Download PDFInfo
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- CN1208134C CN1208134C CN 02146392 CN02146392A CN1208134C CN 1208134 C CN1208134 C CN 1208134C CN 02146392 CN02146392 CN 02146392 CN 02146392 A CN02146392 A CN 02146392A CN 1208134 C CN1208134 C CN 1208134C
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Abstract
The present invention relates to an ammonium and rare earth ion mixed exchange method of a molecular sieve. The method comprises the following steps: a molecular sieve and water are pulped together; an obtained serous fluid is continuously loaded on the filtration fabric of a horizontal belt filter and sequentially passes through a filter cake forming region and an ion exchange region; a filter cake is washed, sucked dry, and detached from the filtration fabric. The molecular sieve is a Y-shaped molecular sieve of once exchange and once roasting; acid and/or salt of which the dosage is 0.1 to 5 wt% of that of the molecular sieve is also added to the serous fluid. The vacuum degree of a liquid receiver in the filter cake forming region ensures that no crazing exists on the surface of the filter cake. In the ion exchange region, a mixed water solution containing ammonium salt and a rare earth compound are added to the upper part of the filter cake, the dosage of the mixed water solution containing the ammonium salt and the rare earth compound enables the weight ratio of the rare earth oxide and the molecular sieve to be 0.01 to 0.2. Measured by ammonium chloride, the weight ratio of the ammonium salt and the molecular sieve is 0.01 to 0.4. The present invention successfully finishes the simultaneous exchange of the ammonium salt and the rare earth compound to the Y-shaped molecular sieve of once exchange and once roasting on the belt filter; the present invention has the advantages of small water consumption, high efficiency and capability of achieving the aim of accurately exchanging quantitative rare earth on the molecular sieve through controlling the proportion of the ammonium salt and the rare earth compound.
Description
Invention field
The invention relates to a kind of ion-exchange process of molecular sieve, more specifically say so about a kind of ammonium and rare earth ion mixing and exchanging method of molecular sieve.
Background technology
Y zeolite is the active component commonly used of catalyst, in the catalyst, prepares by the NaY molecular sieve as Y zeolite contained in the hydrocarbon cracking catalyzer.NaY 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 ammonium ion exchange to reduce sodium content wherein and/or to introduce rare earth ion or other ions directly as the active component of Cracking catalyst.
At present, industrial employing reduces the method that Y zeolite carries out ion-exchange sodium content wherein and/or introduces rare earth ion, and the method for carrying out ion-exchange has two kinds.
First method is with Y zeolite and the aqueous solution making beating that contains ammonium ion and/or 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 the ammonium ion aqueous solution and rare earth ion then from the filter cake top successively, or adding ammonium salt and rare earth compound mixed aqueous solution, under filter cloth in the liquid receiver under the vacuum action, ion-exchange takes place continuously by filter cake the time in solution.The advantage of using band filter is can integrate Separation of Solid and Liquid, 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 continuous mobile and horizontal band filter, this band filter is equipped with a vacuum tank with part separated from each other, wherein, each part separated from each other with one independently the liquid recipient link to each other with vacuum controller.On the filter bag slurries, impose enough vacuum, obtain containing in a kind of space of particle the filter cake thin layer of the lubricous dry of water, when filter cake passes through described vacuum tank 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 a static 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, 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 substantial constant, move the filter bag that slurry is housed continuously, order forms the district by a filter cake, at least one ion-exchange area and a scrubbing section, simultaneously independently impose vacuum on the liquid receiver under the filter bag, unload filter cake from filter bag at each.The method is characterized in that filter cake does not have surface checking 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 filtercondition, 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 surface checking, 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 particles and part molecular sieve.Because one hands in the aqueous slurry of a roasting Y zeolite, the very tiny and reason of handing over roasting Y zeolite self intrinsic property 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 filter bag of going up band filter, formed filter cake is a kind of very filter cake of densification, water penetration extreme difference, the rate of filtration (liquid sees through the speed of filter cake) is quite slow, and ion exchange process can't be carried out.Therefore, still on band filter, do not hand over one to bake the method that Y zeolite carries out ion-exchange in the prior art to one.
Summary of the invention
The ammonium and the rare earth ion mixing and exchanging method that the purpose of this invention is to provide a kind of new not only water-saving efficient but also high molecular sieve.
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 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, top at filter cake adds the mixed aqueous solution that contains ammonium salt and rare earth compound, it is 0.01-0.2 that the consumption of the mixed aqueous solution of ammonium salt-containing and rare earth compound makes the weight ratio of rare earth oxide and molecular sieve, and in ammonium chloride, the weight ratio of ammonium salt and molecular sieve is 0.01-0.4.
Compared with prior art, method provided by the invention has overcome prior art and can not successfully finish on band filter and hand over a roasting Y zeolite to carry out the exchange of ammonium salt and rare earth compound simultaneously to one to a shortcoming of handing over a roasting Y zeolite to carry out ion-exchange on band filter.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.
Method provided by the invention can also reach in the purpose that accurately exchanges quantitative rare earth on the molecular sieve by the ratio of control ammonium salt and rare earth compound, and this is that prior art is beyond one's reach.
The specific embodiment
According to method provided by the invention, described one hands over a roasting Y zeolite to refer to that one hands over a roasting ultra-steady Y molecular sieve USY, one hands over a roasting hydrogen Y molecular sieve HY, to hand over a roasting rare-earth Y molecular sieve REY and to hand among the roasting rare earth hydrogen Y molecular sieve REHY one or more, is preferably one and hands over a roasting ultra-steady Y molecular sieve USY or to hand over a roasting hydrogen Y molecular sieve HY.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 mixes as ammonium chloride, ammonium sulfate solution normally with the sodium Y molecular sieve and the aqueous solution that contains ammonium ion, carries 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 20-90 ℃, 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 temperature of drying, is preferably 100-150 ℃, and sintering 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 inorganic acid and the organic acid one or more, example hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetate, propionic acid, benzoic acid etc., wherein, be preferably hydrochloric acid, sulfuric acid, nitric acid and/or phosphoric acid, more preferably hydrochloric acid or nitric acid.
Described salt refers to one or more in water-soluble various salt, as ammonium, alkali metal, aluminium, iron, the soluble-salt hydrochlorate of rare earth, sulfate, nitrate, in the phosphate one or more, wherein, be preferably alkali metal, ammonium, iron, the hydrochloride of rare earth, in sulfate and the nitrate one or more, as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, sodium sulphate, sodium chloride, in the chloride of sodium nitrate and rare earth one or more, the more preferably hydrochloride of alkali metal and/or ammonium and/or nitrate, particularly sodium chloride, potassium chloride, ammonium chloride, sodium nitrate, in potassium nitrate and the ammonium nitrate 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 10-100 ℃, is preferably 20-90 ℃.
According to method provided by the invention, can reach the purpose of quantitative rare earth in accurate exchange on a friendship one roasting Y zeolite by the ratio of ammonium salt and rare earth compound in the mixed aqueous solution of controlling ammonium salt and rare earth compound.Can hand over a roasting Y zeolite to submit one exactly according to following relational expression and change quantitative rare earth ion:
(1) when one hands over a roasting Y zeolite lattice constant to be the 24.48-24.52 dust,
A=1.48ln{[34.42/ (4.93-b)-1] }-2.87 (formula 1).
(2) to hand over a roasting Y zeolite lattice constant be during greater than the 24.52-24.66 dust when one,
A=0.30ln{[7.17/ (5.51-b)-1] }+0.43 (formula 2).
Wherein, a contains in the mixed aqueous solution of ammonium salt and rare earth compound, in rare earth chloride and ammonium chloride, and the weight ratio of rare earth compound and ammonium salt, b one hands on the roasting Y zeolite after exchange the weight percentage of the rare earth oxide in the exchange.
According to method provided by the invention, in order to make full use of ammonium salt and rare earth compound resource, before ion-exchange area, can also and preferably include a counterflow exchange district, in described counterflow exchange district, above filter cake, the counterflow exchange liquid that adds a kind of ammonium salt-containing and rare earth compound, under the vacuum action under the counterflow exchange district in the liquid receiver, when counterflow exchange liquid sees through filter cake and filter cloth, finish part ammonium ion and rare earth ion exchanged, described counterflow exchange liquid is the exchange waste liquid that ion-exchange area produces, or the waste liquid and the above-mentioned mixed liquor that contains the mixed aqueous solution of ammonium salt and rare earth compound of ion-exchange area generation.Vacuum under the counterflow exchange district in the liquid receiver guarantees to have all the time on the filter cake liquid to exist.
According to a specific embodiments of the present invention, can be by flow implementation the present invention shown in Figure 1.
One, the formation of filter cake
With 1-100 ℃, preferred 20-90 ℃ 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 3 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 rate of loading of slurries should guarantee to form is preferably 0.5-1.5 centimetre at 0.5-2 centimetre.Vacuum in the liquid receiver 5 makes the filter cake surface not have be full of cracks substantially.Vacuum in the liquid receiver 5 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.Wherein, the exchange waste liquid that described 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, ion-exchange
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 10 of ion-exchange area 7 is positioned at the below of filter cloth 3, liquid receiver 10 is vacuumized, and above filter cake, adding temperature by container 8 by pipeline 9 is 10-100 ℃, preferred 20-90 ℃ the ammonium salt-containing and the mixed aqueous solution of rare earth compound.Under vacuum action, the mixed aqueous solution of ammonium salt-containing and rare earth compound has been finished ion-exchange by filter cake the time.
Vacuum in the liquid recipient 10 makes the filter cake surface keep the moistening be full of cracks that do not occur.Vacuum in the liquid recipient 10 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The consumption of the mixed aqueous solution of ammonium salt-containing and rare earth compound and concentration are decided according to measuring on the final Y zeolite middle rare earth oxide.In general, it is 0.01-0.2 that the consumption that contains the mixed aqueous solution of ammonium salt-containing and rare earth compound makes the weight ratio of rare earth oxide and molecular sieve, is preferably 0.01-0.1, and in ammonium chloride, the weight ratio of ammonium salt and molecular sieve is 0.01-0.4, is preferably 0.01-0.2.In oxide, the content of the aqueous solution middle rare earth compound of compounds containing rare earth is the 10-150 grams per liter, is preferably the 20-100 grams per liter, and in ammonium chloride, the concentration of ammonium salt is the 10-150 grams per liter, is preferably the 20-100 grams per liter.The temperature of the aqueous solution of compounds containing rare earth can be 10-100 ℃, is preferably 20-90 ℃.
Described rare earth compound is selected from rare earth solubility salt, as rare earth-iron-boron and/or rare earth nitrades.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.Described ammonium salt is selected from not with the rare earth ion reaction and generates in the ammonium salt of precipitation one or more, as ammonium chloride and/or ammonium nitrate.
If rare earth oxide on wanting quantitatively to exchange should be selected the relation shown in formula 1 or the formula 2 for use according to the difference of molecular sieve lattice constant, adjust the ratio of rare earth ion and ammonium ion in molecular sieve.
Exchange waste liquid in the liquid receiver 8 is by pipeline 11 dischargings, and described exchange waste liquid is used for pulling an oar with molecular sieve.
Three, washing
Washing methods is conventionally known to one of skill in the art.Along with moving of filter cloth 3, filter cake enters scrubbing section 12, at described scrubbing section 12, adds deionized water from container 13 through pipeline 14, simultaneously, liquid receiver 15 is vacuumized, under vacuum action, liquid sees through filter cake, with the survivor ion in the filter cake, and anion flush away particularly.The weight ratio of deionized water and molecular sieve is generally 1-10, is preferably 2-6, and the temperature of deionized water is 10-100 ℃, is preferably 20-90 ℃.
The waste liquid that liquid receiver 15 is collected is discharged through pipeline 16, can be used to prepare the mixed aqueous solution of described ammonium salt-containing and rare earth compound.Vacuum in the liquid receiver 15 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.Along with moving of filter cloth 3, filter cake enters and blots district 17, and in the described district 17 that blots, under the vacuum action, the liquid in the filter cake is by further sucking-off in the liquid receiver 18 under filter cloth 3.Liquid in the liquid receiver 18 is discharged through pipeline 19, and its purposes is identical with liquid in the receiver 15.Vacuum in the liquid receiver 18 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
According to another one specific embodiments of the present invention, can be by flow implementation the present invention shown in Figure 2.
One, the formation of filter cake
With 1-100 ℃, preferred 20-90 ℃ 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 3 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 rate of loading of slurries should guarantee to form is preferably 0.5-1.5 centimetre at 0.5-2 centimetre.Vacuum in the liquid receiver 5 makes the filter cake surface not have be full of cracks substantially.Vacuum in the liquid receiver 5 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Wherein, the exchange waste liquid that described acid and/or salt can be got by the counterflow exchange district 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 9 in counterflow exchange district 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, counterflow exchange
Along with moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters counterflow exchange district 7, in described counterflow exchange district 7, to add temperature from the top of filter cake is 10-100 ℃, is preferably 20-90 ℃, through pipeline 15, from the exchange waste liquid in the liquid receiver under the ion-exchange area 11 14, under vacuum action, described exchange waste liquid has been finished the part ion exchange by filter cake and filter cloth 3 time.Vacuum in the liquid recipient 9 makes the filter cake surface keep the moistening be full of cracks that do not occur.Vacuum in the liquid recipient 9 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The exchange waste liquid that counterflow exchange district 7 obtains is collected by liquid receiver 9, and discharges through pipeline 10, as the source of described acid and/or salt, is used for preparing the molecular sieve pulp that contains acid and/or salt.
Three, ion-exchange
With moving of filter cloth 3, filter cake enters ion-exchange area 11, the liquid receiver 14 of ion-exchange area 11 is positioned at the below of filter cloth 3, liquid receiver 14 is vacuumized, and above filter cake, adding temperature by container 12 by pipeline 13 is 10-100 ℃, preferred 20-90 ℃ the ammonium salt-containing and the mixed aqueous solution of rare earth compound.Under vacuum action, the mixed aqueous solution of ammonium salt-containing and rare earth compound has been finished ion-exchange by filter cake and filter cloth 3 time.
Vacuum in the liquid recipient 14 makes the filter cake surface keep the moistening be full of cracks that do not occur.Vacuum in the liquid recipient 14 is generally the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The consumption of the mixed aqueous solution of ammonium salt-containing and rare earth compound and concentration are decided according to measuring on the final Y zeolite middle rare earth oxide.In general, it is 0.01-0.2 that the consumption that contains the mixed aqueous solution of ammonium salt-containing and rare earth compound makes the weight ratio of rare earth oxide and molecular sieve, is preferably 0.01-0.1, and in ammonium chloride, the weight ratio of ammonium salt and molecular sieve is 0.01-0.4, is preferably 0.01-0.2.In oxide, the content of the aqueous solution middle rare earth compound of compounds containing rare earth is the 10-150 grams per liter, is preferably the 20-100 grams per liter, and in ammonium chloride, the concentration of ammonium salt is the 10-150 grams per liter, is preferably the 20-100 grams per liter.The temperature of the aqueous solution of compounds containing rare earth can be 10-100 ℃, is preferably 20-90 ℃.
Described rare earth compound is selected from rare earth solubility salt, as rare earth-iron-boron and/or rare earth nitrades.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.Described ammonium salt is selected from not with the rare earth ion reaction and generates in the ammonium salt of precipitation one or more, as ammonium chloride and/or ammonium nitrate.
If rare earth oxide on wanting quantitatively to exchange should be selected the relation shown in formula 1 or the formula 2 for use according to the difference of molecular sieve lattice constant, adjust the ratio of rare earth ion and ammonium ion in molecular sieve.
Exchange waste liquid in the liquid receiver 14 is back to counterflow exchange district 7 by pipeline 15.
Four, washing
Washing methods is conventionally known to one of skill in the art.Along with moving of filter cloth 3, filter cake enters scrubbing section 16, at described scrubbing section 16, adds deionized water from container 17 through pipeline 18, simultaneously, liquid receiver 19 is vacuumized, under vacuum action, liquid sees through filter cake, with the survivor ion in the filter cake, and anion flush away particularly.The weight ratio of deionized water and molecular sieve is generally 1-10, is preferably 2-6, and the temperature of deionized water is 10-100 ℃, is preferably 20-90 ℃.
The waste liquid that liquid receiver 19 is collected is discharged through pipeline 20, can be used to prepare the mixed aqueous solution of described ammonium salt-containing and rare earth compound.Vacuum in the liquid receiver 19 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.Along with moving of filter cloth 3, filter cake enters and blots district 21, and in the described district 21 that blots, under the vacuum action, the liquid in the filter cake is by further sucking-off in the liquid receiver 22 under filter cloth 3.Liquid in the liquid receiver 22 is discharged through pipeline 23, and its purposes is identical with liquid in the receiver 19.Vacuum in the liquid receiver 22 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
Existing ammonium ion of this Comparative Examples explanation and rare earth ion mixing and exchanging method.
With a mixed aqueous solution of handing over a roasting ultra-steady Y molecular sieve (lattice constant is 24.52 dusts, and sodium oxide content is 4.3 heavy %, and Qilu Petrochemical company catalyst plant is produced), rare earth chloride and ammonium chloride (contain rare earth oxide 50 grams per liters, wherein, La
2O
3Content is 16.6 grams per liters, CeO
2Content is 29.6 grams per liters, other rare earth oxide content 4.0 grams per liters, ammonium chloride concentration is 100 grams per liters) mix and pull an oar, molecular sieve in the slurries: rare earth oxide: ammonium chloride: water=1: 0.039: 0.06: 10, slurries are warming up to 90 ℃, under agitation carry out ion-exchange 60 minutes, filter the filtrate A1 (standby) and the filter cake that obtain then.The content of rare earth chloride is about 4.5 grams per liters among the filtrate A1, and the content of sodium chloride is about 6 grams per liters, and the content of ammonium chloride is about 15 grams per liters.With temperature is that 90 ℃ of d10 doubly wash the filter cake that obtains to the deionized water 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 rare earth oxide RE
2O
3Content is 1.7 heavy %, wherein, and La
2O
3Content be 0.57 heavy %, CeO
2Content be 1.0 heavy %, the content of other rare earth oxide is 0.13 heavy %, sodium oxide content is 1.2 heavy %.Wherein, molecular sieve middle rare earth oxide content assay method is referring to petrochemical industry analytical method (RIPP test method), p368-370, Science Press, 1990.Sodium oxide content adopts aas determination.
Comparative Examples 2
Existing ammonium ion of this Comparative Examples explanation and rare earth ion mixing and exchanging method.
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 4.0 heavy %, Qilu Petrochemical company catalyst plant is produced) replace Comparative Examples 1 described to hand over a roasting ultra-steady Y molecular sieve, molecular sieve in the slurries: rare earth oxide: ammonium chloride: water=1: 0.042: 0.05: 10, the mixed aqueous solution of rare earth chloride and ammonium chloride contains rare earth oxide 75 grams per liters, wherein, and La
2O
3Content is 62.6 grams per liters, CeO
2Content is 65.6 grams per liters, other rare earth oxide content 6.8 grams per liters, and ammonium chloride concentration is 50 grams per liters.Obtain filtrate A2 (standby) and Y zeolite B2.The content of rare earth chloride is about 4.5 grams per liters among the filtrate A2, and the content of sodium chloride is about 6 grams per liters, and the content of ammonium chloride is about 12 grams per liters.B2 middle rare earth oxide RE
2O
3Content is 4.0 heavy %, wherein La
2O
3Content be 3.34 heavy %, CeO
2Content be 0.3 heavy %, the content of other rare earth oxide is 0.4 heavy %, sodium oxide content is 1.3 heavy %.
Following example adopts cloth formula funnel filter to experimentize, and is used for illustrating method provided by the invention.Owing to adopt cloth formula funnel filter 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, sodium chloride and ammonium chloride contained among the used filtrate A1) is 1.1 heavy % of molecular sieve.The molecular sieve pulp that obtains is heated to 80 ℃, pours in the Buchner funnel, simultaneously filter flask is evacuated to 0.07 MPa, formation thickness is 10 millimeters filter cake on filter cloth.When the no liquid of filter cake surface, adding rare earth oxide content immediately is that 43 grams per liters (each oxide content is with Comparative Examples 1), ammonium chloride concentration are 100 grams per liters, temperature is 70 ℃ rare earth chloride and an ammonium chloride mixed solution (weight ratio of rare earth chloride and ammonium chloride is 0.75 in the mixed solution), adding speed guarantees that the filter cake surface does not form be full of cracks, it is 0.02 that the consumption of rare earth chloride and ammonium chloride mixed solution makes the weight ratio of rare earth oxide and molecular sieve, and the weight ratio of ammonium chloride and molecular sieve is 0.04.When the no liquid of filter cake surface, add temperature immediately and be 70 ℃ deionized water washing leaching 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 rare earth oxide RE
2O
3Content is 2.1 heavy %, wherein La
2O
3Content be 0.70 heavy %, CeO
2The heavy % of content 1.24, the content of other rare earth oxide is 0.16 heavy %, the content of sodium oxide molybdena is 0.8 heavy %, the weight ratio of molecular sieve middle rare earth oxide content and rare earth chloride and ammonium chloride concerns coincidence formula 1 as calculated.
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 150 grams per liters, wherein the consumption of salt (being rare earth chloride, sodium chloride and ammonium chloride contained among the used filtrate A2) is 2 heavy % of molecular sieve.The molecular sieve pulp that obtains is heated to 80 ℃, pours in the Buchner funnel, simultaneously filter flask is evacuated to 0.05 MPa.Formation thickness is 12 millimeters filter cake on filter cloth.When the no liquid of filter cake surface, adding rare earth oxide content immediately is 75 grams per liters, ammonium chloride concentration is 50 grams per liters, temperature is that (weight ratio of rare earth chloride and ammonium chloride is 1 in the mixed aqueous solution for 70 ℃ rare earth chloride and the mixed aqueous solution of ammonium chloride, the ratio of each rare earth oxide is with Comparative Examples 2), adding speed guarantees that the filter cake surface does not form be full of cracks, it is 00.05 that the consumption of rare earth chloride and ammonium chloride mixed aqueous solution makes the weight ratio of rare earth oxide and molecular sieve, in ammonium chloride, the weight ratio of ammonium salt and molecular sieve is 0.033, and adding speed guarantees that the filter cake surface does not form be full of cracks.When the no liquid of filter cake surface, add temperature immediately and be 80 ℃ deionized water washing leaching 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 hydrogen Y zeolite Z2.Z2 middle rare earth oxide RE
2O
3Content be 4.65 heavy %, wherein La
2O
3Content be 3.88 heavy %, CeO
2Content be 0.35 heavy %, the content of other rare earth oxide is 0.42 heavy %, the content of sodium oxide molybdena is 0.8 heavy %.The weight ratio of molecular sieve middle rare earth oxide content and rare earth chloride and ammonium chloride concerns coincidence formula 2 as calculated.
Example 3
This example illustrates the applicable cases of method provided by the invention on the commercial plant band filter.
By flow process shown in Figure 1, Comparative Examples 2 described is handed over a roasting hydrogen Y zeolite, 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 1.2 heavy % of molecular sieve consumption.When the exchange waste liquid amount that produces in the liquid receiver 10 is enough, replace hydrochloric acid fully with the exchange waste liquid, it is 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 ℃, are 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, and 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 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 10 is housed, and the vacuum in the liquid receiver 10 is 0.04 MPa.Is 60 ℃ from the container 8 on filter cake top by pipeline 9 adding temperature, and rare earth oxide content is 75 grams per liters (ratio of each rare earth oxide is with Comparative Examples 1), and ammonium chloride content is the rare earth chloride of 50 mol and the mixed aqueous solution of ammonium chloride.It is 0.05 that the consumption of described solution makes the weight ratio of rare earth oxide and molecular sieve, and the weight ratio of ammonium chloride and molecular sieve is 0.033.Exchange waste liquid in the liquid receiver 10 is used for joining making beating jar 1, as the source of described acid and/or salt.
Along with moving of filter cloth, filter cake leaves ion-exchange area 7 and enters scrubbing section 12.Adding temperature from the container 13 on filter cake top by pipeline 14 is 60 ℃ deionized water, and under the vacuum action, liquid is through filter cake liquid receiver 15 in, and the ion that flush away is residual, the consumption of deionized water are 3 times of molecular sieve weight.Vacuum in the liquid receiver 15 is 0.05 MPa.Scrub raffinate in the liquid receiver 15 is discharged from pipeline 16, and mixes with liquid from liquid receiver 18, and being used for preparing above-mentioned rare earth oxide content is 75 grams per liters, and ammonium chloride content is the rare earth chloride of 50 mol and the mixed aqueous solution of ammonium chloride.
After washing finishes, filter cake continues to move ahead under the drive of filter cloth, enter and blot district 17, under the vacuum action in liquid receiver 18, the liquid in the filter cake is by further sucking-off, and the vacuum of liquid receiver 18 is 0.04 MPa, the waste liquid of collecting in the liquid receiver 18 is discharged through pipeline 19, and mix with liquid from liquid receiver 15, being used for preparing above-mentioned rare earth oxide content is 75 grams per liters, ammonium chloride content is the rare earth chloride of 50 mol and the mixed aqueous solution of ammonium chloride.At the filter cloth turning, filter cake and filter cloth are peeled off.Dry filter cakes for 120 ℃, obtain containing the Y zeolite Z3 of rare earth.The content of sodium oxide molybdena is 0.9 heavy % among the Z3, and the content of rare earth oxide is 4.7 heavy %.Wherein, La
2O
3Content be 1.57 heavy %, CeO
2Content be 2.78 heavy %, the content of other rare earth oxide is 0.36 heavy %.The weight ratio of molecular sieve middle rare earth oxide content and rare earth chloride and ammonium chloride concerns coincidence formula 2 as calculated.
Example 4
This example explanation applicable cases of method on the commercial plant band filter that contains counterflow exchange provided by the invention.
By flow process shown in Figure 2, Comparative Examples 2 described is handed over a roasting hydrogen Y zeolite, 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 1.2 heavy % of molecular sieve consumption.When the exchange waste liquid amount that produces in the liquid receiver 9 is enough, replace hydrochloric acid fully with the exchange waste liquid, it is 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 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 1 centimetre 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 counterflow exchange district 7 that liquid receiver 9 is housed, and the vacuum in the liquid receiver 9 is 0.04 MPa.Add the exchange waste liquid that comes from pipeline 15 and liquid receiver 14 from the pipeline 8 on filter cake top, this exchange waste liquid comes from ion-exchange area 11.Exchange waste liquid in the liquid receiver 9 can join in the making beating jar 1, as the source of described acid and/or salt by pipeline 10.
Along with moving of filter cloth, enter ion-exchange area 11, the mixed liquor that adds rare earth chloride and ammonium chloride solution from container 12 through pipeline 13, this mixed liquor contain 75 grams per liters rare earth oxide and the ammonium chloride of 50 grams per liters (weight ratio of rare earth chloride and ammonium chloride is 1 in the mixed aqueous solution, the ratio of each rare earth oxide is with example 1), it is 0.05 that the consumption of mixed liquor makes the weight ratio of rare earth oxide and molecular sieve, and the weight ratio of ammonium chloride and molecular sieve is 0.033.Vacuum in the liquid receiver 14 is 0.04 MPa, and whole process filter cake surface has liquid to exist.The whole adverse currents of exchange waste liquid that liquid receiver 14 is collected are to counterflow exchange district 7.
Along with moving of filter cloth, filter cake leaves ion-exchange area 11 and enters scrubbing section 16.From the container 17 on filter cake top, adding temperature by pipeline 18 is 60 ℃ deionized water, and under the vacuum action, liquid is through filter cake liquid receiver 19 in, and the ion that flush away is residual, the consumption of deionized water are 3 times of molecular sieve weight.Vacuum in the liquid receiver 19 is 0.05 MPa.Scrub raffinate in the liquid receiver 19 is discharged from pipeline 20, and mixes with waste liquid in the liquid receiver 22, and being used for preparing above-mentioned rare earth oxide content is that 75 grams per liters, ammonium chloride content are the mixed liquor of 50 grams per liters.
After washing finished, filter cake continued to move ahead under the drive of filter cloth, entered to blot district 21.Under the vacuum action in liquid receiver 22, the liquid in the filter cake is by further sucking-off, and the vacuum of liquid receiver 22 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 Z3 of rare earth.The content of sodium oxide molybdena is 0.9 heavy % among the Z3, and the content of rare earth oxide is 4.7 heavy %.Wherein, La
2O
3Content be 1.57 heavy %, CeO
2Content be 2.78 heavy %, the content of other rare earth oxide is 0.36 heavy %.Liquid in the liquid receiver 22 is discharged from pipeline 23, mixes with liquid in the liquid receiver 19, and being used for preparing above-mentioned rare earth oxide content is that 75 grams per liters, ammonium chloride content are the mixed liquor of 50 grams per liters.The weight ratio of molecular sieve middle rare earth oxide content and rare earth chloride and ammonium chloride concerns coincidence formula 2 as calculated.
Claims (12)
1. the ammonium of a molecular sieve and rare earth ion mixing and exchanging method, 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 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, top at filter cake adds the mixed aqueous solution that contains ammonium salt and rare earth compound, it is 0.01-0.2 that the consumption of the mixed aqueous solution of ammonium salt-containing and rare earth compound makes the weight ratio of rare earth oxide and molecular sieve, in ammonium chloride, the weight ratio of ammonium salt and molecular sieve is 0.01-0.4.
2. method according to claim 1, it is characterized in that, described one hands over a roasting Y zeolite to refer to that one hands over a roasting ultra-steady Y molecular sieve USY, and one hands over a roasting hydrogen Y molecular sieve HY, to hand over a roasting rare-earth Y molecular sieve REY and to hand among the roasting rare earth hydrogen Y molecular sieve REHY one or more.
3. method according to claim 2 is characterized in that, described one hands over a roasting Y zeolite to refer to that one hands over a roasting ultra-steady Y molecular sieve USY or to hand over a roasting hydrogen Y molecular sieve HY.
4. method according to claim 1 is characterized in that described acid is selected from one or more in hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetate, propionic acid, the benzoic acid.
5. method according to claim 1 is characterized in that, described salt is selected from one or more in the soluble-salt hydrochlorate, sulfate, nitrate, phosphate of ammonium, alkali metal, aluminium, iron, rare earth.
6. method according to claim 5 is characterized in that described salt is selected from one or more in sodium chloride, potassium chloride, ammonium chloride, sodium nitrate, potassium nitrate and the ammonium nitrate.
7. 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.
8. method according to claim 1 is characterized in that, it is 0.01-0.1 that the consumption of the mixed aqueous solution of ammonium salt-containing and rare earth compound makes the weight ratio of rare earth oxide and molecular sieve, and in ammonium chloride, the weight ratio of ammonium salt and molecular sieve is 0.01-0.2.
9. method according to claim 1 is characterized in that, describedly is selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more on rare.
10. method according to claim 9 is characterized in that, described rare earth is selected from lanthanum, cerium, the lanthanum rich mixed rare earth or rich cerium mix rare ±.
11. method according to claim 1 is characterized in that, described rare earth compound is selected from rare earth-iron-boron and/or rare earth nitrades, and described ammonium salt is selected from as ammonium chloride and/or ammonium nitrate.
12. method according to claim 1, it is characterized in that, before ion-exchange area, also comprise a counterflow exchange district, in described counterflow exchange district, above filter cake, the counterflow exchange liquid that adds a kind of ammonium salt-containing and rare earth compound, under the vacuum action under the counterflow exchange district in the liquid receiver, when counterflow exchange liquid sees through filter cake and filter cloth, finish part ammonium ion and rare earth ion exchanged, described counterflow exchange liquid is the exchange waste liquid that ion-exchange area produces, or the waste liquid and the described mixed liquor that contains the mixed aqueous solution of ammonium salt and rare earth compound of ion-exchange area generation, the vacuum under the counterflow exchange district in the liquid receiver guarantees to have all the time on the filter cake liquid to exist.
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|---|---|---|---|
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