CN1216687C - Exchange method of rare earth ion for molecular sieve - Google Patents
Exchange method of rare earth ion for molecular sieve Download PDFInfo
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- CN1216687C CN1216687C CN 02130782 CN02130782A CN1216687C CN 1216687 C CN1216687 C CN 1216687C CN 02130782 CN02130782 CN 02130782 CN 02130782 A CN02130782 A CN 02130782A CN 1216687 C CN1216687 C CN 1216687C
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Abstract
The present invention relates to an exchange method of rare earth (RE) ions for a molecular sieve, which comprises the following steps: a serous fluid which contains a molecular sieve and has a pH value of 2 to 7 is continuously loaded to filtration fabric of a horizontal belt filter; the filtration fabric loaded with the serous fluid which contains the molecular sieve sequentially passes through a filter cake forming region, an ion exchange region and a washing region; then, the filtration fabric is sucked dry, detached and dried; finally, the exchanged filter cake of the molecular sieve is obtained. In the ion exchange region, a water solution of an RE compound at a temperature of 10 to 100 DEG C is added to the upper part of the filter cake, the dosage of the water solution of RE compounds enables the weight ratio of an RE oxide to the molecular sieve is 0.01 to 0.2. The method provided by the present invention has the maximal advantages of no RE precipitation generation, and the filtration fabric can be used for a long time. The method provided by the present invention also has the advantages of high degree of exchange automation, water saving and high efficiency.
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
The molecular sieve that contains rare earth is various catalyzer, active ingredient commonly used as cracking catalyst, it is usually by being that the sodium type molecular sieve that is not less than 1 heavy % carries out ion-exchange with rare earth compound solution with sodium content, perhaps the mixed aqueous solution with ammonium-containing compound and rare earth compound carries out ion-exchange, with the filtration cakes torrefaction that obtains or moist, roasting and obtaining then.
Change more rare earth in order to submit at molecular sieve, do not wish that the cation-bit on the molecular sieve is occupied by ammonium ion, in this case, usually do not use the mixed aqueous solution of ammonium-containing compound and rare earth compound, but directly sodium type molecular sieve is carried out ion-exchange with the rare earth compound aqueous solution.
The method of molecular sieve being carried out rare earth ion exchanged has two kinds.
First method is with sodium type molecular sieve and the making beating of rare earth compound aqueous solution, 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 sodium type molecular sieve is mixed the water slurry that making beating forms a kind of molecular sieve with water, this slurry directly is loaded on the filter cloth of band filter, on filter cloth, form certain thickness filter cake, add the aqueous solution of rare earth compound 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 solution.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.
But, according to the top described method rare earth compound aqueous solution, when sodium type molecular sieve is carried out rare earth ion exchanged, precipitation process slowly can appear, these sedimentary particles are very little, be easy to stop up the mesh of belt filter filter cloth, filtration procedure can't be finished, ion exchange process also can't go on certainly.
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 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 the method that a kind of fluidization zeolite granular carries out ion-exchange continuously, 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.
US 3,943, though 233 described methods have provided the general method that carries out ion-exchange on band filter, and, how sodium type molecular sieve is carried out rare earth ion exchanged and does not specify.
Summary of the invention
The objective of the invention is to overcome the shortcoming that existing molecular sieve RE ion exchange method stops up the filter cloth mesh easily, a kind of RE ion exchange method of molecular sieve of new difficult obstruction filter cloth mesh is provided.
As mentioned above, according to the existing method rare earth compound aqueous solution recited above, when on the belt filter, sodium type molecular sieve being carried out rare earth ion exchanged, precipitation process slowly can appear, these sedimentary particles are very little, be easy to stop up the mesh of belt filter filter cloth, filtration procedure can't be finished, ion exchange process also can't go on certainly.After deliberation, the present inventor finds, these precipitations are the precipitations that contain rare earth compound, the reason that causes these precipitations to form is that the water slurry of sodium type molecular sieve is alkalescence, thereby the filter cake that forms on the belt filter also is alkalescence, and under alkaline condition, the rare earth compound aqueous solution easily forms above-mentioned precipitation, according to above-mentioned discovery, the present inventor has invented following method.
Method provided by the invention comprises and contains with a kind of that molecular sieve pulp is continuous to be loaded on the filter cloth of horizontal belt filter, the filter cloth that is mounted with molecular sieve pulp is formed the district by a filter cake in proper order, an ion-exchange area and a washing section, blot, unload and the dry filter cake that obtains, wherein, described molecular sieve is the sodium type molecular sieve that sodium oxide content is not less than 1 heavy %, contain molecular sieve pulp pH value and be 2-7, temperature is 10-100 ℃; Form the district at described filter cake, under filter cloth in the liquid receiver under the vacuum action, liquid in the slurries sees through filter cloth, and the molecular sieve in the slurries forms filter cake on the filter step, and 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, from the top adding temperature of filter cake is the aqueous solution of 10-100 ℃ rare earth compound, under filter cloth in the liquid receiver under the vacuum action, when the aqueous solution of rare earth compound sees through filter cake and filter cloth, finished rare earth ion exchanged, it is 0.01-0.2 that the consumption of the rare earth compound aqueous solution makes the weight ratio of rare earth oxide and molecular sieve, and the vacuum tightness in the described ion-exchange area liquid receiver guarantees to have on the filter cake surface liquid to exist.
The great advantage of method provided by the invention is when having overcome prior art and on band filter sodium type molecular sieve being carried out rare earth ion exchanged, precipitation process slowly can occur, is easy to stop up the shortcoming of the mesh of belt filter filter cloth.Adopt method provided by the invention, do not have the rare earth compound precipitation to produce, filter cloth can life-time service.
Method provided by the invention is to carry out on the belt filter, therefore, has certainly and carries out exchange level of automation height that ion-exchange had, water-saving, advantage that efficient is high on the belt filter.
Description of drawings
Fig. 1 and Fig. 2 all are schematic flow sheets of method provided by the invention.
Embodiment
According to method provided by the invention, the pH value of described molecular sieve pulp is preferably 3-6.The pH value of described slurries obtains by add acidic substance in the alkaline molecular sieve slurries.The crystallization material that obtains after the crystallization when alkaline molecular sieve slurries can be synthesis of molecular sieve can be the alkaline slurry that the making beating of sodium type molecular sieve and water or other alkalescence or neutral solution forms.Described acidic substance are selected from not with rare earth compound and form in the sedimentary various acidic substance one or more, as not forming in precipitation mineral acid and the organic acid one or more with rare earth compound, are preferably hydrochloric acid and/or nitric acid.
According to method provided by the invention, described molecular sieve can be the molecular sieve that the sodium oxide content of natural or synthetic is not less than 1 heavy %, as in faujusite, ZSM series zeolite, mordenite, BETA zeolite, omega zeolite, A type zeolite, zeolite L, phosphate aluminium molecular sieve, the HTS one or more, one or more in X type zeolite, y-type zeolite, ZSM-5 zeolite, mordenite, BETA zeolite, the omega zeolite particularly.Sodium oxide content in the described molecular sieve is preferably the heavy % of 3-15.It is that the NaY zeolite of the heavy % of 3-15 carries out the y-type zeolite that the rare earth ion exchanged preparation contains rare earth that method provided by the invention especially is fit to sodium oxide content.
The described temperature that contains the slurries of molecular sieve is 10-100 ℃, is preferably 20-80 ℃.The solid content of described molecular sieve pulp can be the 50-200 grams per liter, is preferably the 50-150 grams per liter.It is 0.5-2 centimetre that described molecular sieve pulp is loaded into the thickness that speed on the filter cloth makes filter cake form the filter cake that the district forms, and is preferably 0.5-1.5 centimetre.
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, and in general, the vacuum tightness that described filter cake forms in district's liquid receiver is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The temperature of the aqueous solution of described rare earth compound is 10-100 ℃, is preferably 20-80 ℃.In the aqueous solution of described rare earth compound, the content of rare earth compound is not particularly limited, as long as guarantee that it is 0.01-0.2 that the aqueous solution of rare earth compound is used for making the weight ratio of rare earth oxide and molecular sieve, is preferably 0.05-0.17 and gets final product.In general, in the aqueous solution of described rare earth compound, rare earth oxide content is the 10-120 grams per liter, is preferably the 30-100 grams per liter.
In order to guarantee that filter cake does not chap, vacuum tightness in the described ion-exchange area liquid receiver guarantees to have on the filter cake surface liquid to exist, in general, the vacuum tightness in the described ion-exchange area liquid receiver is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Described rare earth compound is selected from one or more in the water-soluble various rare earth compounds of energy, as rare earth chloride, and one or more in the nitrate of rare earth.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 method of described washing is conventionally known to one of skill in the art, at described washing section, adding temperature on the top of filter cake is 10-100 ℃, the deionized water or the pH value that are preferably 20-80 ℃ are 2-7, be preferably the sour water of 3-6, under filter cloth in the liquid receiver under the vacuum action, described deionized water or sour water when seeing through filter cake, flush away foreign ion and unnecessary rare earth ion.The add-on of described deionized water or sour water is 1-10 a times of molecular sieve weight, is preferably 2-6 doubly.In order to guarantee that filter cake does not chap, the vacuum tightness in the washing section liquid receiver guarantees to have on the filter cake surface liquid to exist, and in general, the vacuum tightness in the described washing section liquid receiver is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Described sour water can be decationized Y sieve water, also can be that decationized Y sieve water or exhaustion of yin cationic water get by adding hydrochloric acid adjusting pH value.
After unloading filter cake, filter cloth needs to clean, and cleans the used water of filter cloth and generally uses above-mentioned sour water.In order to save the consumption of water, the sour water that described first washing section and second washing section are used can and preferably adopt the sour water behind the washing filter cloth.
The described method that blots is conventionally known to one of skill in the art, blots as described can blot the district by one by the filter cake after will washing and finish, and in the described district that blots, under the liquid receiver under the effect of vacuum, the water in the filter cake is sucked out under filter cloth.
According to the described exsiccant condition of method provided by the invention is conventionally known to one of skill in the art.In general, described exsiccant temperature can be 100-300 ℃, preferred 120-200 ℃.
According to method provided by the invention, be fully used and exchange more rare earth ion for the aqueous solution that makes rare earth compound, before described ion-exchange area, preferably include a countercurrent exchange district.In described countercurrent exchange district, top at filter cake, adding a kind of temperature is the pre-exchange liquid of 10-100 ℃ compounds containing rare earth, under the vacuum action under filter cloth in the liquid receiver, the pre-exchange liquid of described compounds containing rare earth is finished the part rare earth ion exchanged when seeing through filter cake and filter cloth.Vacuum tightness in the described liquid receiver guarantees to have on the filter cake surface liquid to exist, and in general, the pre-exchange liquid of described compounds containing rare earth is the exchange waste liquid of collecting in the ion-exchange area liquid receiver.Vacuum tightness in the described countercurrent exchange district liquid receiver is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
According to specific embodiment of the present invention, can be according to flow implementation the present invention shown in Figure 1.
One. filter cake forms the district.
As shown in Figure 1, with temperature is 10-100 ℃, be preferably 20-80 ℃, the pH value is loaded on the filter cloth 3 of horizontal belt filter through pipeline 2 from making beating jar 1 continuously for the slurries that contain molecular sieve of 2-7, and described molecular sieve is the sodium type molecular sieve that sodium oxide content is not less than 1 heavy %.
Filter cloth moves into filter cake formation district 4 continuously, and under the vacuum action, the liquid in the slurries sees through filter cloth 3 in 3 times liquid receivers 5 of filter cloth, and the formation thickness on the filter step 3 of the molecular sieve in the slurries is 0.5-2 centimetre filter cake.The vacuum tightness that described filter cake forms in district's 4 liquid receivers 5 guarantees not have be full of cracks substantially on the filter cake surface, and in general this vacuum tightness is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Filter cake forms the waste liquid of district's 4 formation and collects in liquid receiver 5, and discharges through pipeline 6.
Two, ion-exchange area.
Along with moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters ion-exchange area 7.At described ion-exchange area 7, top from filter cake 3, adding temperature from container 8 through pipeline 9 is 10-100 ℃, be preferably 20-80 ℃ the rare earth compound aqueous solution, in 3 times liquid receivers 10 of filter cloth under the vacuum action, when the rare earth compound aqueous solution sees through filter cake and filter cloth 3, finished rare earth ion exchanged, it is 0.01-0.2 that the consumption of the rare earth compound aqueous solution makes the weight ratio of rare earth oxide and molecular sieve.In the described rare earth compound aqueous solution, rare earth oxide content is the 10-120 grams per liter, is preferably the 30-100 grams per liter.In order to guarantee that filter cake does not chap, the vacuum tightness in the described ion-exchange area liquid receiver 10 guarantees to have on the filter cake surface liquid to exist, and in general this vacuum tightness is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The exchange waste liquid that ion-exchange area 7 forms is collected in liquid receiver 10, and discharges through pipeline 11.The exchange waste liquid of collecting in the liquid receiver 10 can be used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pull an oar, and preparation contains the slurries of molecular sieve.
Three, washing section.
Along with moving of filter cloth 3, the filter cake after exchange enters washing section 12.At described washing section 12, is 10-100 ℃ from container 13 through pipeline 14 adding temperature from the top of filter cake, the deionized water or the pH value that are preferably 20-80 ℃ are 2-7, be preferably the sour water of 3-6, in 3 times liquid receivers 15 of filter cloth under the vacuum action, when deionized water or sour water see through filter cake and filter cloth 3, flush away foreign ion and unnecessary ammonium ion and rare earth ion, the consumption of deionized water or sour water is 1-10 a times of molecular sieve weight, is preferably 2-6 doubly.In order to guarantee that filter cake does not chap, the vacuum tightness in described washing section 12 liquid receivers 15 guarantees to have on the filter cake surface liquid to exist, and in general this vacuum tightness is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The scrub raffinate that washing section 12 forms is collected in liquid receiver 15, and discharges through pipeline 16.The scrub raffinate of collecting in the liquid receiver 15 can be used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pull an oar, and preparation contains the slurries of molecular sieve, also can be used for preparing the above-mentioned rare earth compound aqueous solution as exchange liquid.
Four, blot the district.
Along with moving of filter cloth 3, the filter cake after washing enters and blots district 17.In the described district 17 that blots, under the vacuum action, the liquid in the filter cake is sucked out in 3 times liquid receivers 18 of filter cloth, obtains the less filter cake of water-content.Vacuum tightness in the liquid receiver 18 is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Blotting the waste liquid that obtains of district collects in liquid receiver 18, and through pipeline 19 discharges, be used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pull an oar, preparation contains the slurries of molecular sieve, also can be used for preparing the above-mentioned rare earth compound aqueous solution as exchange liquid.
Five, unload filter cake and drying.
Along with moving of filter cloth 3, the filter cake after blotting falls and is collected in the corner of filter cloth 3 and be dry, and the exsiccant temperature can be 100-300 ℃, is preferably 120-200 ℃.
According to another one specific embodiment of the present invention, can be according to flow implementation the present invention shown in Figure 2.
One. filter cake forms the district.
As shown in Figure 2, with temperature is 10-100 ℃, be preferably 20-80 ℃, the pH value is loaded on the filter cloth 3 of horizontal belt filter through pipeline 2 from making beating jar 1 continuously for the slurries that contain molecular sieve of 2-7, and described molecular sieve is the sodium type molecular sieve that sodium oxide content is not less than 1 heavy %.
Filter cloth moves into filter cake formation district 4 continuously, and under the vacuum action, the liquid in the slurries sees through filter cloth 3 in 3 times liquid receivers 5 of filter cloth, and the formation thickness on the filter step 3 of the molecular sieve in the slurries is 0.5-2 centimetre filter cake.The vacuum tightness that described filter cake forms in district's 4 liquid receivers 5 guarantees not have be full of cracks substantially on the filter cake surface, and in general this vacuum tightness is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Filter cake forms the waste liquid of district's 4 formation and collects in liquid receiver 5, and discharges through pipeline 6.The slurries of collecting in the liquid receiver 5 can be used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pull an oar, and preparation contains the slurries of molecular sieve, also can be used as dust catching liquid.
Two, countercurrent exchange district.
Along with moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters countercurrent exchange district 20, in described countercurrent exchange district 20, top at filter cake, the pre-exchange liquid that adds a kind of compounds containing rare earth from pipeline 11, under the vacuum action in 3 times liquid receivers 21 of filter cloth, the pre-exchange liquid of described compounds containing rare earth is finished the part rare earth ion exchanged when seeing through filter cake and filter cloth 3.The pre-exchange liquid of the compounds containing rare earth in the described pipeline 11 is the exchange waste liquids from the ion-exchange area of liquid receiver 10.
In order to guarantee that filter cake does not chap, vacuum tightness in described countercurrent exchange district 20 liquid receivers 21 guarantees to have on the filter cake surface liquid to exist, vacuum tightness in the 20 times liquid receivers 21 in described countercurrent exchange district is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The exchange waste liquid that countercurrent exchange district 20 forms is collected in liquid receiver 21, and discharges through pipeline 22.The exchange waste liquid of collecting in the liquid receiver 21 is used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pulls an oar, and preparation contains the slurries of molecular sieve.
Two, ion-exchange area.
Along with moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters ion-exchange area 7, at described ion-exchange area 7, top from filter cake 3, adding temperature from container 8 through pipeline 9 is 10-100 ℃, be preferably 20-80 ℃ the rare earth compound aqueous solution, in 3 times liquid receivers 10 of filter cloth under the vacuum action, when the rare earth compound aqueous solution sees through filter cake and filter cloth 3, finished rare earth ion exchanged, it is 0.01-0.2 that the consumption of the rare earth compound aqueous solution makes the weight ratio of rare earth oxide and molecular sieve.In the described rare earth compound aqueous solution, rare earth oxide content is the 10-120 grams per liter, is preferably the 30-100 grams per liter.In order to guarantee that filter cake does not chap, the vacuum tightness in the described ion-exchange area liquid receiver 10 guarantees to have on the filter cake surface liquid to exist, and in general this vacuum tightness is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The exchange waste liquid that ion-exchange area 7 forms is collected in liquid receiver 10, and through pipeline 11 adverse currents to countercurrent exchange district 20.
Three, washing section.
Along with moving of filter cloth 3, the filter cake after exchange enters washing section 12.At described washing section 12, is 10-100 ℃ from container 13 through pipeline 14 adding temperature from the top of filter cake, the deionized water or the pH value that are preferably 20-80 ℃ are 2-7, be preferably the sour water of 3-6, in 3 times liquid receivers 15 of filter cloth under the vacuum action, when deionized water or sour water see through filter cake and filter cloth 3, flush away foreign ion and unnecessary rare earth ion, the consumption of deionized water or sour water is 1-10 a times of molecular sieve weight, is preferably 2-6 doubly.In order to guarantee that filter cake does not chap, the vacuum tightness in 12 times liquid receivers 15 of described washing section guarantees to have on the filter cake surface liquid to exist, and in general this vacuum tightness is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
The scrub raffinate that washing section 12 forms is collected in liquid receiver 15, and discharges through pipeline 16.The scrub raffinate of collecting in the liquid receiver 15 can be used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pull an oar, and preparation contains the slurries of molecular sieve, also can be used for preparing the above-mentioned rare earth compound aqueous solution as exchange liquid.
Four, blot the district.
Along with moving of filter cloth 3, the filter cake after washing enters and blots district 17, and in the described district 17 that blots, under the vacuum action, the liquid in the filter cake is sucked out in 3 times liquid receivers 18 of filter cloth, obtains the less filter cake of water-content.Vacuum tightness in the liquid receiver 18 is the 0.01-0.08 MPa, is preferably the 0.02-0.07 MPa.
Blotting the waste liquid that obtains of district collects in liquid receiver 18, and through pipeline 19 discharges, be used for being not less than 1 molecular sieve that weighs % with above-mentioned sodium oxide content and pull an oar, preparation contains the slurries of molecular sieve, also can be used for preparing the above-mentioned rare earth compound aqueous solution as exchange liquid.
Five, unload filter cake and drying.
Along with moving of filter cloth 3, the filter cake after blotting falls and is collected in the corner of filter cloth 3 and be dry, and the exsiccant temperature can be 100-300 ℃, is preferably 120-200 ℃.。
The following examples will be described further present method, but therefore not limit the present invention.
Comparative Examples 1
This Comparative Examples illustrates the RE ion exchange method of existing molecular sieve as the tripping device analoging industrial device with B.
Owing to adopt cloth formula funnel filtration unit also to experience filter cake formation, ion-exchange (or the countercurrent exchange before 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.
One, filter cake forms.
(sodium oxide content is 14.0 heavy % with the NaY zeolite, lattice constant is 24.66 dusts, the Qilu Petrochemical catalyst plant is produced) mix with deionized water and pull an oar that to be prepared into the pH value be 9, solid content is the slurries of 100 grams per liters, the slurries that obtain under agitation are heated to 70 ℃, pour B into, simultaneously, the filter flask of B is evacuated to 0.05 MPa.Under vacuum action, on the filter cloth of B, form the filter cake of about 1.2 cm thicks of one deck, the waste liquid in the emptying filter flask.
Two, ion-exchange.
Keep the vacuum tightness in the filter flask, in the time of will be on the filter cake surface without liquid, slowly add temperature immediately and be 65 ℃ and contain rare earth oxide 50 grams per liters (wherein, lanthanum trioxide accounts for 83.4 heavy % of total amount of the rare earth oxide, cerium oxide accounts for 7.5 heavy % of total amount of the rare earth oxide, other rare earth oxide accounts for 9.1 heavy % of total amount of the rare earth oxide) rare earth chloride solution, the speed that adds makes the filter cake surface have liquid to exist all the time, and making the weight ratio of rare earth oxide and molecular sieve up to the aqueous solution that adds is 0.14.
Three, washing.
Keep the vacuum tightness in the filter flask, in the time of will be on the filter cake surface without liquid, slowly add temperature immediately and be 65 ℃ deionized water, the speed that adds deionized water makes the filter cake surface have liquid to exist all the time, up to 3 times the deionized water that adds the molecular sieve weight that is equivalent in the filter cake.
Four, blot.
Continue to vacuumize the filter cake after do not have liquid from funnel, to flow out, obtaining blotting.
Five, unload filter cake and drying.
From funnel, take out filter cloth, and unload filter cake,, obtain containing the Y zeolite of rare earth 140 ℃ of oven dry from filter cloth.Adopt " petrochemical complex analytical procedure (RIPP test method) ", p 368-370, Science Press, rare earth oxide content and sodium oxide content in the rare-earth-containing molecular sieve that method of describing in 1990 and aas determination obtain.The result is as follows: rare earth oxide content is 14.0 heavy % (wherein, lanthanum trioxide 11.7 heavy %, cerium oxide 1.05 heavy %, other rare earth oxide 1.27 heavy %), and sodium oxide content is 4.3 heavy %.
Comparative Examples 2
This Comparative Examples illustrates the RE ion exchange method of existing molecular sieve as the tripping device analoging industrial device with B.
The same block of filter cloth that uses Comparative Examples 1 to use repeats the operating process of Comparative Examples 1, and along with multiplicity increases, filter cloth is more and more yellow, and when repeating the 6th time, filtration velocity is obviously slack-off, and when being repeated to the 9th time, filtration can't be carried out.
Example 1
This example illustrates method provided by the invention with B as the tripping device analoging industrial device.
One, filter cake forms.
NaY zeolite (with Comparative Examples 1) is mixed making beating, and to be prepared into the pH value be 9 with deionized water, and solid content is the slurries of 80 grams per liters.In the slurries that obtain, add hydrochloric acid, regulate the pH value to 6.0 of slurries, the slurries that obtain under agitation are heated to 70 ℃, pour the B that is placed with the filter cloth identical into, simultaneously, the filter flask of B is evacuated to 0.04 MPa with Comparative Examples 1 material.Under vacuum action, on the filter cloth of B, form the filter cake of about 1.2 cm thicks of one deck, the waste liquid in the emptying filter flask.
Two, ion-exchange.
Keep the vacuum tightness in the filter flask, in the time of will be on the filter cake surface without liquid, slowly add temperature immediately and be 65 ℃ and contain rare earth oxide 80 grams per liters (wherein, lanthanum trioxide accounts for 83.4 heavy % of total amount of the rare earth oxide, cerium oxide accounts for 7.5 heavy % of total amount of the rare earth oxide, other rare earth oxide accounts for 9.1 heavy % of total amount of the rare earth oxide) rare earth chloride solution, the speed that adds makes the filter cake surface have liquid to exist all the time, and making the weight ratio of rare earth oxide and molecular sieve up to the mishmetal aqueous solution that adds is 0.14.
Three, washing.
Keep the vacuum tightness in the filter flask, in the time of will be on the filter cake surface without liquid, slowly add temperature immediately and be 65 ℃ deionized water, the speed that adds deionized water makes the filter cake surface have liquid to exist all the time, up to 3 times the deionized water that adds the molecular sieve weight that is equivalent in the filter cake.
Four, blot.
Continue to vacuumize the filter cake after do not have liquid from funnel, to flow out, obtaining blotting.
Five, unload filter cake and drying.
From funnel, take out filter cloth, and unload filter cake,, obtain containing the Y zeolite of rare earth 120 ℃ of oven dry from filter cloth.In this molecular sieve, rare earth oxide content is 14.8 heavy % (wherein, lanthanum trioxide 12.3 heavy %, cerium oxide 1.11 heavy %, other rare earth oxide 1.34 heavy %), and sodium oxide content is 4.0 heavy %.
Example 2
This example illustrates method provided by the invention with B as the tripping device analoging industrial device.
The same block of filter cloth that use-case 1 uses repeats above-mentioned entire operation process, and when repeating the 30th time, the filter cloth color does not still change, and filtration velocity is still with for the first time identical.
Example 3-6
Following example illustrates method provided by the invention with B as the tripping device analoging industrial device.
Method by example 1 is carried out rare earth ion exchanged to the NaY molecular sieve, and different is, the acid of adding adds the pH value of sour rear slurry, the temperature of slurries, and the weight ratio of rare earth oxide and molecular sieve, the temperature of deionized water is different with consumption.The acid that adds adds the pH value of sour rear slurry, the temperature of slurries, and the weight ratio of rare earth oxide and molecular sieve, the temperature of deionized water and consumption are distinguished as shown in table 1.The rare-earth-containing molecular sieve middle-weight rare earths oxide compound and the sodium oxide content that obtain are as shown in table 2.
Table 1
| Example number | 3 | ?4 | ?5 | ?6 |
| The acid that adds | Hydrochloric acid | Hydrochloric acid | Nitric acid | Nitric acid |
| Slurry pH value | 3 | ?5 | ?3 | ?5 |
| The temperature of slurries, ℃ | 50 | ?70 | ?60 | ?80 |
| The weight ratio of rare earth oxide and molecular sieve | 0.15 | ?0.16 | ?0.148 | ?0.16 |
| The temperature of deionized water, ℃ | 40 | ?80 | ?40 | ?80 |
| The consumption of deionized water | 2 times of molecular sieve weight | 4 times of molecular sieve weight | 3 times of molecular sieve weight | 5 times of molecular sieve weight |
Table 2
| Example number | 3 | ?4 | ?5 | ?6 |
| Rare earth oxide content, heavy % | 14.8 | ?14.5 | ?14.3 | ?14.6 |
| Lanthanum trioxide content, heavy % | 12.3 | ?12.1 | ?11.9 | ?12.5 |
| Cerium oxide content, heavy % | 1.11 | ?1.09 | ?1.07 | ?1.14 |
| Other rare earth oxide content, heavy % | 1.34 | ?1.32 | ?1.30 | ?1.38 |
| Sodium oxide content, heavy % | 4.2 | ?4.3 | ?4.0 | ?4.0 |
Example 7
This example illustrates the result that method provided by the invention is implemented on the technical scale band filter.
One. filter cake forms the district.
As shown in Figure 1, with NaY zeolite (with Comparative Examples 1) and deionized water (when the amount of the waste liquid of collecting in the liquid receiver 10,15,18 is enough, change the waste liquid in the liquid receiver 10,15,18 into, or its mixed solution) being blended in the making beating jar 1 making beating, to be prepared into the pH value be 9, and solid content is the slurries of 100 grams per liters.Adding hydrochloric acid in the slurries that obtain, regulate the pH value to 5.5 of slurries, is that 5.5 slurries are heated to 75 ℃ with obtaining the pH value, then, is loaded into continuously through pipeline 2 on the filter cloth 3 of horizontal belt filter.
Filter cloth moves into filter cake continuously and forms district 4, in 3 times liquid receivers 5 of filter cloth under the vacuum action, liquid in the slurries sees through filter cloth 3, and the molecular sieve in the slurries forms filter cake on the filter step 3, and the speed of loading makes the thickness of the filter cake that forms on filter cloth 3 be 1.2 centimetres.The vacuum tightness that described filter cake forms in district's 4 liquid receivers 5 is 0.05 MPa.
Filter cake forms the waste liquid of district's formation and collects in liquid receiver 5, and discharges through pipeline 6, is used as dust catching liquid.
Two, ion-exchange area.
Along with moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters ion-exchange area 7.At described ion-exchange area 7, from the top of filter cake 3, adding temperature from container 8 through pipeline 9 is the aqueous solution of 75 ℃ rare earth chloride, in 3 times liquid receivers 10 of filter cloth under the vacuum action, when the aqueous solution of rare earth chloride sees through filter cake and filter cloth 3, finished rare earth ion exchanged.Contain rare earth oxide 50 grams per liters (wherein containing lanthanum trioxide 16.7 grams per liters, cerium oxide 29.5 grams per liters, other rare earth oxide 3.8 grams per liters) in the aqueous solution of rare earth chloride (every gram rare earth oxide can generate 1.5 gram rare earth chlorides).It is 0.15 that the consumption of the aqueous solution of rare earth chloride makes the weight ratio of rare earth oxide and molecular sieve.Vacuum tightness in the described ion-exchange area liquid receiver 10 is 0.05 MPa, in the whole exchange process, has liquid to exist on the filter cake surface all the time.
The exchange waste liquid that ion-exchange area 7 forms is collected in liquid receiver 10, and discharges through pipeline 11, is used for and above-mentioned NaY molecular sieve making beating, and preparation contains the slurries of molecular sieve
Three, washing section.
Along with moving of filter cloth 3, the filter cake after exchange enters washing section 12.At described washing section 12, adding temperature from container 13 through pipeline 14 from the top of filter cake is that 20 ℃ pH value is 4 sour water, in 3 times liquid receivers 15 of filter cloth under the vacuum action, when sour water sees through filter cake and filter cloth 3, flush away foreign ion and unnecessary rare earth ion, the consumption of sour water are 3 times of molecular sieve weight.Vacuum tightness in described washing section 12 liquid receivers 15 is 0.05 MPa.In the whole washing process, there is liquid to exist on the filter cake surface all the time.
The scrub raffinate that washing section 12 forms is collected in liquid receiver 15, and discharges through pipeline 16, is used for and the making beating of above-mentioned NaY molecular sieve, prepares the slurries that contain molecular sieve, or is mixed with the aqueous solution of above-mentioned rare earth chloride with rare earth chloride.
Four, blot the district.
Along with moving of filter cloth 3, the filter cake after washing enters and blots district 17, and in the described district 17 that blots, under the vacuum action, the liquid in the filter cake is sucked out in 3 times liquid receivers 18 of filter cloth.Vacuum tightness in the liquid receiver 18 is 0.05 MPa.
Blot the waste liquid that obtains of district and in liquid receiver 18, collects, and discharge, be used for and the making beating of above-mentioned NaY molecular sieve, prepare the slurries that contain molecular sieve, or be mixed with the aqueous solution of above-mentioned rare earth chloride with rare earth chloride through pipeline 19.
Five, unload filter cake and drying.
Along with moving of filter cloth 3, the filter cake after blotting falls and is collected in the corner of filter cloth 3.The filter cake that obtains 150 ℃ of oven dry, is obtained containing the Y zeolite of rare earth, and its rare earth oxide content is 14.5 heavy % (wherein, lanthanum trioxide 4.84 heavy %, cerium oxide 8.56 heavy %, other rare earth oxide 1.10 heavy %), and sodium oxide content is 4.2 heavy %.
Continuous operation is handled 13 tons in NaY molecular sieve every day according to the method described above, and filter cloth does not still stop up sign after 60 days.
Comparative Examples 3
The RE ion exchange method of the existing molecular sieve of this Comparative Examples explanation.
Method by example 7 is carried out rare earth ion exchanged to same NaY molecular sieve, and different does not just add hydrochloric acid, and directly using the pH value is 9 molecular sieve pulp.Continuous operation after 1 day filter cloth stop up fully, can not finish filtration procedure.
Example 8
This example illustrates the result that method provided by the invention is implemented on the technical scale band filter.
One. filter cake forms the district.
As shown in Figure 2, with NaY zeolite (with Comparative Examples 1) and deionized water (when the amount of the waste liquid of collecting in the liquid receiver 21,15,18 is enough, change the waste liquid of the one in the liquid receiver 21,15,18 into, or its mixed solution) being blended in the making beating jar 1 making beating, to be prepared into the pH value be 9, and solid content is the slurries of 120 grams per liters.Adding hydrochloric acid in the slurries that obtain, regulate the pH value to 4.5 of slurries, is that 4.5 slurries are heated to 75 ℃ with obtaining the pH value, then, is loaded into continuously through pipeline 2 on the filter cloth 3 of horizontal belt filter.
Filter cloth moves into filter cake continuously and forms district 4, in 3 times liquid receivers 5 of filter cloth under the vacuum action, liquid in the slurries sees through filter cloth 3, and the molecular sieve in the slurries forms filter cake on the filter step 3, and the speed of loading makes the thickness of the filter cake that forms on filter cloth 3 be 1 centimetre.The vacuum tightness that described filter cake forms in district's 4 liquid receivers 5 is 0.05 MPa.
Filter cake forms the waste liquid of district's 4 formation and collects in liquid receiver 5, and discharges through pipeline 6, is used as dust catching liquid.
Two, countercurrent exchange district.
Along with moving of filter cloth 3, the filter cake that forms district's 4 formation at filter cake enters countercurrent exchange district 20, in described countercurrent exchange district 20, top at filter cake, add a kind of pre-exchange liquid through pipeline 11, under the vacuum action in 3 times liquid receivers 21 of filter cloth, described pre-exchange liquid has been finished the part rare earth ion exchanged when seeing through filter cake and filter cloth 3.Described pre-exchange liquid is through the exchange waste liquid of pipeline 11 from the ion-exchange area of liquid receiver 10.
Vacuum tightness 0.05 MPa in described countercurrent exchange district 20 liquid receivers 21.In whole countercurrent exchange process, there is liquid to exist on the filter cake surface all the time.
The exchange waste liquid that countercurrent exchange district 20 forms is collected in liquid receiver 21, and discharges through pipeline 22.The exchange waste liquid of collecting in the liquid receiver 21 is used for and above-mentioned NaY molecular sieve making beating, and preparation contains the slurries of molecular sieve.
Three, ion-exchange area.
Along with moving of filter cloth 3, filter cake after the exchange of countercurrent exchange district enters ion-exchange area 7, at described ion-exchange area 7, top from filter cake 3, adding temperature from container 8 through pipeline 9 is the aqueous solution of 20 ℃ rare earth chloride, in 3 times liquid receivers 10 of filter cloth under the vacuum action, when the aqueous solution of rare earth chloride sees through filter cake and filter cloth 3, finished rare earth ion exchanged.Contain rare earth oxide 80 grams per liters (wherein in the aqueous solution of rare earth chloride (every gram rare earth oxide can generate 1.5 gram rare earth chlorides), lanthanum trioxide accounts for 83.4 heavy % of total amount of the rare earth oxide, cerium oxide accounts for 7.5 heavy % of total amount of the rare earth oxide, and other rare earth oxide accounts for 9.1 heavy % of total amount of the rare earth oxide).It is 0.16 that the consumption of the aqueous solution of rare earth chloride makes the weight ratio of rare earth oxide and molecular sieve.Vacuum tightness in the described ion-exchange area liquid receiver 10 is 0.05 MPa, in the whole exchange process, has liquid to exist on the filter cake surface all the time.
The exchange waste liquid that ion-exchange area 7 forms is collected in liquid receiver 10, and enters countercurrent exchange district 20 through pipeline 11.
Four, washing section.
Along with moving of filter cloth 3, filter cake after exchange enters washing section 12, at described washing section 12, adding temperature from container 13 through pipeline 14 from the top of filter cake is 50 ℃ deionized water, in 3 times liquid receivers 15 of filter cloth under the vacuum action, when deionized water saw through filter cake and filter cloth 3, flush away foreign ion and unnecessary rare earth ion, the consumption of deionized water were 3 times of molecular sieve weight.Vacuum tightness in described washing section 12 liquid receivers 15 is 0.05 MPa.In the whole washing process, there is liquid to exist on the filter cake surface all the time.
The scrub raffinate that washing section 12 forms is collected in liquid receiver 15, and discharges through pipeline 16.The scrub raffinate of collecting in the liquid receiver 15 is used for preparing above-mentioned aqueous solution of rare earth chloride as exchange liquid.
Five, blot the district.
Along with moving of filter cloth 3, the filter cake after washing enters and blots district 17, and in the described district 17 that blots, under the vacuum action, the liquid in the filter cake is sucked out in 3 times liquid receivers 18 of filter cloth.Vacuum tightness in the liquid receiver 18 is 0.06 MPa.
Blot the waste liquid that obtains of district and in liquid receiver 18, collects, and discharge, be used for preparing above-mentioned as the aqueous solution of rare earth chloride that exchanges liquid through pipeline 19.
Five, unload filter cake and drying.
Along with moving of filter cloth 3, the filter cake after blotting falls and is collected in the corner of filter cloth 3.The filter cake that obtains 150 ℃ of oven dry, is obtained containing the Y zeolite of rare earth.Its rare earth oxide content is 15.5 heavy % (wherein, lanthanum trioxide 12.9 heavy %, cerium oxide 1.16 heavy %, other rare earth oxide 1.41 heavy %), and sodium oxide content is 4.0 heavy %.
Continuous operation is handled 10 tons in NaY molecular sieve every day according to the method described above, and filter cloth does not still stop up sign after 60 days.
Claims (20)
1. the RE ion exchange method of a molecular sieve, this method comprises and containing on the filter cloth that molecular sieve pulp is loaded into horizontal belt filter continuously a kind of, the filter cloth that is mounted with molecular sieve pulp is formed the district by a filter cake in proper order, an ion-exchange area and a washing section blot, and unload and the dry filter cake that obtains, it is characterized in that, described molecular sieve is the sodium type molecular sieve that sodium oxide content is not less than 1 heavy %, and the pH value that contains molecular sieve pulp is 2-7, and temperature is 10-100 ℃; Form the district at described filter cake, under filter cloth in the liquid receiver under the vacuum action, liquid in the slurries sees through filter cloth, and the molecular sieve in the slurries forms filter cake on the filter step, and 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, from the top adding temperature of filter cake is the aqueous solution of 10-100 ℃ rare earth compound, under filter cloth in the liquid receiver under the vacuum action, when the aqueous solution of rare earth compound sees through filter cake and filter cloth, finished rare earth ion exchanged, it is 0.01-0.2 that the consumption of the rare earth compound aqueous solution makes the weight ratio of rare earth oxide and molecular sieve, and the vacuum tightness in the described ion-exchange area liquid receiver guarantees to have on the filter cake surface liquid to exist.
2. method according to claim 1 is characterized in that, the pH value of described molecular sieve pulp is 3-6.
3. method according to claim 1, it is characterized in that, the pH value of described slurries obtains by add acidic substance in the alkaline molecular sieve slurries, and described acidic substance are selected from not with rare earth compound and form in the sedimentary various acidic substance one or more.
4. method according to claim 3 is characterized in that, described acidic substance are hydrochloric acid and/or nitric acid.
5. method according to claim 1 is characterized in that, described molecular screening one or more in faujusite, ZSM series zeolite, mordenite, BETA zeolite, omega zeolite, A type zeolite, zeolite L, phosphate aluminium molecular sieve, HTS.
6. method according to claim 5 is characterized in that, described molecular screening one or more in X type zeolite, y-type zeolite, ZSM-5 zeolite, mordenite, BETA zeolite, omega zeolite.
7. method according to claim 1 is characterized in that, the sodium oxide content in the described molecular sieve is the heavy % of 3-15.
8. method according to claim 1 is characterized in that the described temperature that contains the slurries of molecular sieve is 20-80 ℃.
9. method according to claim 1, the solid content that it is characterized in that described molecular sieve pulp is the 50-200 grams per liter.
10. method according to claim 9, the solid content that it is characterized in that described molecular sieve pulp is the 50-150 grams per liter.
11. method according to claim 1 is characterized in that, it is 0.2-2 centimetre that described molecular sieve pulp is loaded into the thickness that speed on the filter cloth makes filter cake form the filter cake that the district forms.
12. method according to claim 11 is characterized in that, it is 0.5-1.5 centimetre that described molecular sieve pulp is loaded into the thickness that speed on the filter cloth makes filter cake form the filter cake that the district forms.
13. 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.
14. method according to claim 1 is characterized in that, described rare earth compound the temperature of the aqueous solution be 20-80 ℃.
15. method according to claim 1 is characterized in that, it is 0.05-0.17 that the consumption of the aqueous solution of described rare earth compound makes the weight ratio of rare earth oxide and molecular sieve
16. method according to claim 1 is characterized in that, the vacuum tightness in the described ion-exchange area liquid receiver is the 0.01-0.08 MPa.
17. method according to claim 1 is characterized in that, described rare earth compound is selected from rare earth chloride, one or more in the nitrate of rare earth.
18., it is characterized in that described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium according to claim 1 or 17 described methods.
19. method according to claim 18 is characterized in that, described rare earth is selected from lanthanum, cerium, lanthanum rich mischmetal or cerium-rich mischmetal.
20. method according to claim 1, it is characterized in that, before described ion-exchange area, also comprise a countercurrent exchange district, in described countercurrent exchange district, top at filter cake, adding a kind of temperature is the pre-exchange liquid of 10-100 ℃ compounds containing rare earth, under the vacuum action under filter cloth in the liquid receiver, the pre-exchange liquid of described compounds containing rare earth is when seeing through filter cake and filter cloth, finish the part rare earth ion exchanged, vacuum tightness in the described liquid receiver guarantees to have on the filter cake surface liquid to exist, the pre-exchange liquid of described compounds containing rare earth is the exchange waste liquid of collecting in the ion-exchange area liquid receiver, and the vacuum tightness in the described countercurrent exchange district liquid receiver is the 0.01-0.08 MPa.
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