CN1951816A - Deep sealumination modified Y zeolite preparation method - Google Patents
Deep sealumination modified Y zeolite preparation method Download PDFInfo
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Abstract
The invention discloses a preparing method of deep aluminium-stripping Y-zeolite, which comprises the following steps: adopting NH4NaY with the content of Na2O not more than 2.5w%; proceeding first water heat disposal; utilizing high-density H+ ammonium salt solution to exchange to strip aluminium; proceeding second water heat disposal; removing non-frame aluminium through acid solution; setting the disposing temperature of second water heat disposal higher than the first one; improving crystallinity and silicon-aluminium rate with abundant secondary hole.
Description
Technical field
The present invention relates to a kind of preparation method of deep sealumination modified Y zeolite, especially for the preparation method of the deep sealumination modified Y zeolite of the cracking component of medium oil type hydrocracking catalyst.
Background technology
Medium oil type hydrocracking catalyst requires to have higher middle distillates oil selectivity, adopts the main carrier of amorphous aluminum silicide as acidic components, be favourable to the middle distillates oil selectivity that improves catalyzer, but the lytic activity of catalyzer is very low, causes temperature of reaction too high.Make medium oil type hydrocracking catalyst both have good middle distillates oil selectivity, have higher activity again, as the acidic cleavage component of catalyzer, modified zeolite is crucial.Therefore optionally remove the part framework aluminum to reduce the acid site density of zeolite, the secondary pore that obtains to enrich by advanced treatment spreads to help reaction product, reduces second pyrolysis; In modifying process, make zeolite keep higher degree of crystallinity and surface-area, suitably retained part stronger acid sites, then be very important to improving activity of such catalysts.
CN1042523A discloses a kind of hydrothermal dealumination and chemical dealuminization and has combined and be used alternatingly the method for producing the high silica alumina ratio Y zeolite, it comprises mixes with a kind of y-type zeolite containing ammonium ion and mineral acid, at 25～100 ℃, best 50～95 ℃ of dealuminzations 0.5～3 hour, best 1～2 hour, carry out ion-exchange in the dealumination process simultaneously, with sodium ion in the ammonium ion exchange zeolite, and then with the NH that obtains
4Y zeolite carries out dealuminzation with mineral acid or other dealumination agents, carries out steam-treated subsequently, repeats successively once to several times with the process of sour dealuminzation and steam dealumination.Y zeolite raw material wherein can be the NaY zeolite that contains the crystallization NaY of mother liquor or do not contain mother liquor.Although this method can directly use the NaY zeolite as raw material zeolite to be carried out dealuminzation, be easy to the thermostability variation that causes the structure deteriorate of zeolite or make zeolite.US5,013,699 has introduced a kind of treatment process of Y zeolite, is with the NH after the steam-treated
4The NaY zeolite carries out the ammonium exchange under the condition of pH＜4, use HNO in this process
3Regulate pH.The modified Y zeolite that this method obtains is not suitable as the cracking component of middle oil type hydrocracking catalyst because secondary pore is less, and silica alumina ratio is lower.US5,059,567 discloses a kind of method for preparing sealumination modified Y zeolite, and this method is as (NH with NaY zeolite and ammonium ion solution
4)
2SO
4Carry out one or many ion-exchange, then washing, drying; Zeolite after the ammonium ion exchange is calcined in 550～800 ℃ in the presence of steam, this zeolite and then and ammonium ion solution carry out ion-exchange, and calcining again in same temperature ranges stated; Dealuminzation obtains desired SiO by contacting with mineral acid with resulting zeolite then
2/ Al
2O
3The zeolite of mol ratio.Adopt the sealumination modified Y zeolite degree of crystallinity and the surface-area of this method preparation all not high enough.
Summary of the invention
Deficiency at existing technology of preparing, it is big to the invention provides a kind of dealumination depth, it is good that degree of crystallinity keeps, be suitable as the acidic components of medium oil type hydrocracking catalyst, can make catalyzer have the preparation method of excellent middle oil selectivity and lytic activity and good nitrogen resistance modified Y zeolite.
Deep sealumination modified Y zeolite preparation method of the present invention comprises following content:
(1) gets SiO
2/ Al
2O
3Mol ratio is 4.5～8.0, Na
2The NH of O content≤2.5w%
4The NaY zeolite is a raw material, carries out the hydrothermal treatment consists first time;
(2) zeolite that step (1) is obtained is with containing NH
4 +And H
+The mixing solutions exchanging zeolite in Na
+Remove part non-framework aluminum in the zeolite simultaneously, H in the mixing solutions
+Concentration be 0.05～0.6mol/L, NH
4 +Concentration be 0.5～3.0mol/L;
(3) zeolite that step (2) is obtained carries out the hydrothermal treatment consists second time;
(4) zeolite that step (3) is obtained removes non-framework aluminum in the zeolite with acid solution.
Deep sealumination modified Y zeolite preparation method of the present invention specifically may further comprise the steps:
1, with SiO
2/ Al
2O
3Mol ratio is 4.5～8.0, Na
2The NH of O content≤2.5w%
4The NaY zeolite carries out hydrothermal treatment consists.The hydrothermal treatment consists temperature is 500～700 ℃, and water vapor pressure is 0.01～1.0MPa, and the treatment time is 1.0～10.0 hours.
2, the zeolite that step 1 is obtained is with containing NH
4 +And H
+The mixing solutions exchanging zeolite in Na
+Remove part non-framework aluminum in the zeolite simultaneously, H in the mixing solutions
+Concentration be 0.05～0.6mol/L, NH
4 +Concentration be 0.5～3.0mol/L, the exchange temperature is 70～120 ℃, the concentration of exchange slurries mesolite is 0.1～0.5g/ml, exchange and dealuminzation time are 0.5～3.0 hour, exchange and the step of dealuminzation can repeat 1～4 time, make the SiO of Y zeolite
2/ Al
2O
3Mol ratio is 8.0～25.0, removes mother liquor, washes drying then with water.
3, the zeolite that step 2 is obtained carries out the hydrothermal treatment consists second time, the hydrothermal treatment consists temperature is 500～800 ℃, water vapor pressure is 0.01～1.0MPa, treatment time is 1.0～10.0 hours, for the second time the hydrothermal treatment consists temperature is higher than for the first time 10～200 ℃ of hydrothermal treatment consists temperature, preferably is higher than 30～150 ℃.
4, the zeolite that step 3 is obtained removes non-framework aluminum in the zeolite with acid solution.This step can adopt conventional treatment process, can select hydrochloric acid, nitric acid, carbonic acid, sulfuric acid, acetic acid, oxalic acid or citric acid etc. as acid solution, the dealuminzation temperature is generally 60～120 ℃, time was generally 0.5～5 hour, acid concentration is generally 0.1～3mol/L, and the concentration of chemical dealuminization slurries mesolite is 0.05～1.0g/ml.
NH described in the step 2
4 +Can derive from ammonium chloride, ammonium nitrate, volatile salt, ammonium sulfate, ammonium acetate, ammonium oxalate or ammonium citrate etc., H
+Can derive from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid or citric acid etc.
The Y zeolite that the inventive method obtains has following feature: SiO
2/ Al
2O
3Mol ratio is 50～120, lattice constant 2.420～2.435nm, relative crystallinity 〉=90%, specific surface area 750～850m
2/ g, Na
2O content≤0.15w%, the secondary pore of 1.7～10nm account for total pore volume more than 50%, and infrared acidity is 0.10～0.50mmol/g, loading capacity＜0.05, and at 25 ℃, P/P
0Be under 1.0 conditions, the adsorptive capacity＜5.0w% of water.
Compare with the modified Y zeolite of prior art for preparing, the deep sealumination modified Y zeolite of the inventive method preparation has dealumination depth and can choose at random SiO
2/ Al
2O
3Mol ratio is to reach 120 crystalline structure that also do not destroy zeolite, and the deep sealumination modified Y zeolite of the inventive method preparation has the degree of crystallinity height, and surface-area is big, the silica alumina ratio height, lattice constant is little, and secondary pore is abundant, acid site density is low, characteristics such as the acid site ratio height of medium tenacity.Deep sealumination modified Y zeolite is used for medium oil type hydrocracking catalyst, high-ratio surface and flourishing secondary pore have not only promoted the performance of hydrogenation activity, and help the diffusion of reaction product, holding the charcoal ability also greatly strengthens, secondary pore is many, acid site density is low then reduced excessive fragmentation and second pyrolysis occurrence probability, thereby can make catalyzer have excellent middle oil selectivity, the degree of crystallinity height, the acid site ratio height of medium tenacity then makes catalyzer have good activity, the silica alumina ratio height, lattice constant is little, Stability Analysis of Structures, heat and good hydrothermal stability then make catalyzer have good stability.The twice hydrothermal treatment consists process (water for the second time hydrothermal treatment consists temperature be higher than for the first time hydrothermal treatment consists) of the present invention by adopting differing temps helps keeping higher degree of crystallinity under the situation that dealumination depth improves.One skilled in the art will appreciate that the skeleton structure that hydrothermal treatment consists can break away from zeolite framework aluminium zeolite become non-framework aluminum, therefore destroyed to a certain extent zeolite structured, so the hydrothermal treatment consists temperature should not be too high generally speaking.But hydrothermal treatment consists temperature and dealumination depth have direct relation, and this has just formed the contradiction between dealumination depth and the structure deteriorate.The present invention passes through the hydrothermal treatment consists of twice different condition, and cooperates the high density H between the hydrothermal treatment consists twice
+The ammonium salt solution exchange process, promptly reached the ideal dealumination depth, kept zeolite structured again preferably, make the modified zeolite product have good use properties.Hydrothermal treatment consists is carried out under relatively low temperature for the first time, help zeolite structured stable, improve degree of crystallinity, hydrothermal treatment consists is carried out under higher relatively temperature for the second time, help improving dealumination depth, and because its raw material is the zeolite that tends towards stability through hydrothermal treatment consists, a structure, its this can not reduce the degree of crystallinity of zeolite significantly.High density H
+Ammonium salt solution help dealumination process, help improving the silica alumina ratio of Y zeolite.
Be suitable as the acidic cleavage component of medium oil type hydrocracking catalyst with the deep sealumination modified Y zeolite of the inventive method preparation, have excellent middle oil selectivity with the catalyzer of deep sealumination modified Y zeolite preparation of the present invention, good is active and stable.Further specify the solution of the present invention and effect below by example.
Embodiment
Example 1
Get 50 gram NH
4The NaY zeolite (produce, SiO by Wenzhou catalyst plant
2/ Al
2O
3Mol ratio is 5.1, lattice constant a
0=2.470, degree of crystallinity is 95%, Na
2O is 2.3w%, and butt is 70w%.) place heat treatment furnace, control 500 ℃/hour temperature rise rate, temperature is risen to 600 ℃, the water vapor pressure of keeping system simultaneously is 0.15MPa, handles 2.0 hours, sample is taken out in cooling.With containing NH
4 +And H
+Concentration solution (ammonium chloride and the hydrochloric acid mixed solution) 300ml that is respectively 2.0mol/L and 0.2mol/L contact and stir with sample, keep slurry temperature at 90 ℃, constant temperature 1.5 hours, the same terms re-treatment 1 time, filter cake washes with water; Wet cake is placed heat treatment furnace, temperature is risen to 650 ℃, the control water vapor pressure is 0.20MPa, constant temperature 3 hours, and sample is taken out in cooling; Final sample is that the hydrochloric acid of 0.5mol/L removes the non-framework aluminum in the sample with 200ml concentration, and the dealuminzation condition is to handle 2 hours at 80 ℃, obtains product A.The physico-chemical property of product A sees Table 1.
Example 2
Get 50 gram NH
4NaY zeolite (with example 1) places heat treatment furnace, controls 500 ℃/hour temperature rise rate, and temperature is risen to 650 ℃, and the steam partial pressure of keeping system simultaneously is 0.05MPa, handles 3.0 hours, and sample is taken out in cooling; With containing NH
4 +And H
+Concentration solution (ammonium nitrate and the nitric acid mixing solutions) 300ml that is respectively 1.0mol/L and 0.1mol/L contact and stir with sample, keep slurry temperature at 120 ℃, constant temperature 1.0 hours, the same terms re-treatment 1 time, filter cake washes with water; Wet cake is placed heat treatment furnace, temperature is risen to 750 ℃, and water vapor pressure is 0.05MPa in the control stove, constant temperature 3 hours, sample is taken out in cooling; Final sample is that the nitric acid of 0.3mol/L removes the non-framework aluminum in the sample with 200ml concentration, and the dealuminzation condition is to handle 3 hours down at 70 ℃, obtains product B.The physico-chemical property of product B sees Table 1.
Example 3
1. with 2kg NH
4NaY zeolite (with example 1) places heat treatment furnace, in 2 hours temperature is risen to 650 ℃, injects water vapor (with steam rate 3.0kg/h), and keeps system pressure at 0.1MPa, and 650 ℃ of following constant temperature 3.5 hours, sample was taken out in cooling;
2. in autoclave, add entry 15kg, industrial NH
4NO
32.4kg, HNO
33.2kg with the zeolite sample after the thermal treatment for the first time, stirring is started in sealing, and temperature is risen to 120 ℃, constant temperature was handled 1 hour, and filter cake the same terms is handled 1 time again, and the elimination mother liquor is dried to cake moisture ≯ 25%.
3. sample places heat treatment furnace, and 1. condition carries out the secondary hydrothermal treatment consists with step, and wherein the hydrothermal treatment consists temperature is 680 ℃, and the hydrothermal treatment consists time is 3 hours.
4. zeolite sample carries out chemical dealuminization with the HCl of 14 liters of 0.6mol/L under 90 ℃, the elimination mother liquor, and filter cake extremely detects less than Cl with deionized water wash
-, obtain zeolite product C.The physico-chemical property of products C sees Table 1.
Example 4
1. 300g NH
4NaY zeolite (with example 1) places heat treatment furnace, at 1 hour temperature is risen to 550 ℃, keeps pressure at 0.1MPa by zeolite self water vapor, constant temperature 5 hours, and zeolite sample is taken out in cooling.
2. with containing NH
4 +And H
+Concentration solution (ammonium nitrate and the nitric acid mixing solutions) 200ml that is respectively 2.0mol/L and 0.15mol/L contact and stir with sample, temperature is risen to 90 ℃, and kept 2 hours, repeat 2 times, filter cake washs with water purification, drying.
3. zeolite sample is placed in the heat treatment furnace, at 1.5 hours temperature is raised to 680 ℃, feeds water vapor 300g/h simultaneously, and Controlling System pressure is at 0.1 ± 0.02MPa, and the Controlling System temperature kept 6 hours at 680 ℃, and sample is taken out in cooling then.
4. zeolite sample removed non-framework aluminum 1 hour with the HCl 200ml of 0.6mol/L at 95 ℃, and the dealuminzation step repeats 2 times, obtains product D, and the physico-chemical property of product D sees Table 1.
Reference example 5
Get the NH of 3000ml 2mol/L
4Cl solution adds HCl the pH of solution is transferred to 2.0, mix with 300g NaY zeolite and stir, temperature is risen to 90 ℃, constant temperature 2 hours, the elimination mother liquor, filter cake was handled 1 hour at 90 ℃ with the HCl solution of 3000ml0.3mol/L, suction filtration, washing, wet cake places heat treatment furnace in 1.5 hours temperature to be risen to 650 ℃, keep the pressure of system at 0.15MPa with the water vapor of self, constant temperature 2.5 hours, zeolite sample were handled suction filtration with the HCl solution of 3000ml 0.3mol/L 1 hour at 90 ℃ again, washing, wet cake places heat treatment furnace in 1.5 hours temperature to be risen to 650 ℃, the pressure of keeping system with the water vapor of self is at 0.15MPa, and constant temperature 2.5 hours obtains product E.The physico-chemical property of product E sees Table 1.①
Reference example 6
1. NaY zeolite 100g is with (the NH of 2mol/L
4)
2SO
41000ml carries out ammonium exchange 3 times under 90 ℃, each 2 hours, filter cake was used deionized water wash, drying at last.
2. dried sample places heat treatment furnace, in 1.5 hours temperature is risen to 700 ℃, and feeds water vapor (250g/h), constant temperature 2.0 hours, and sample is taken out in cooling then.
3. sample is with (the NH of 2mol/L
4)
2SO
41000ml carries out ammonium exchange 2 times under 90 ℃, each 2 hours, filter cake was used deionized water wash, drying at last.
4. dried sample places heat treatment furnace, in 1.5 hours temperature is risen to 700 ℃, and feeds water vapor (250g/h), constant temperature 2.0 hours, and sample is taken out in cooling then.
5. sample is with the H of 0.4mol/L
2SO
4750ml obtained product F in 1.0 hours at 90 ℃ of following dealuminzations.The physico-chemical property of product F sees Table 1.
The physico-chemical property of table 1 modified Y zeolite A～E
| Example | 1 | 2 | 3 | 4 | 5 | 6 |
| Zeolite numbering SiO 2/Al 2O 3(mol ratio) degree of crystallinity % lattice constant nm specific surface area m 2/g Na 2The infrared acidity mmol/g water adsorption amount of Ow% secondary pore %, 25 ℃ of P/P 0＝0.1w％ | A 53.0 93 2.428 824 0.01 52.4 0.29 3.2 | B 68.2 91 2.430 817 0.01 54.3 0.31 3.1 | C 57.7 96 2.429 829 0.01 55.1 0.23 2.7 | D 113.0 100 2.425 846 0.01 55.6 0.17 2.4 | E 46.0 76 2.430 783 0.01 38.2 0.22 2.9 | F 40.3 73 2.431 741 0.01 40.4 0.25 3.5 |
Example 7～12
Modified Y zeolite A, B, C, D, E, F with example 1～7 are the acidic cleavage component, with the amorphous silicon aluminium is carrier, make tackiness agent with aluminum oxide, with metal W and Ni is the hydrogenation activity component, adopt conventional kneading method moulding, adopt the pickling process carrying metal to be prepared into middle oil type hydrocracking catalyst CA, CB, CC, CD, CE, the CF of example 7～12.Modified Y zeolite A, B, C, D, E, the F content in catalyzer is 15w%.The physico-chemical property of catalyzer sees Table 2.
The physico-chemical property of table 2 catalyzer
| Example | 1 | 2 | 3 | 4 | 5 | 6 |
| Catalyzer numbering chemical constitution, w% WO 3NiO Si-Al-O physico-chemical property pore volume, the ml/g specific surface area, m 2/ g bulk density, g/cm 3 | CA 23.6 6.5 surpluses 0.310 236 0.97 | CB 24.0 6.4 surpluses 0.324 233 0.98 | CC 23.1 6.1 surpluses 0.315 231 0.97 | CD 23.8 6.4 surpluses 0.312 238 0.99 | CE 23.7 6.2 surpluses 0.281 213 0.98 | CF 24.1 6.5 surpluses 0.279 209 0.97 |
Catalyzer CA, the CB of example 7～12, CC, CD, CE, the evaluation of CF reactivity worth adopt one-stage serial once by flow process, carry out on small-sized hydrocracking testing apparatus.VGO is a raw material with triumph, and stock oil character is listed in table 3.
Table 3 triumph VGO main character
| Stock oil | Triumph VGO |
| Density (20 ℃), g/cm 3Boiling range, ℃ IBP/50%/EBP condensation point, ℃ carbon residue, w% S, w% N, w% BMCI value | 0.9138 350/453/560 35 0.20 0.77 0.23 44.6 |
Table 4 has been listed the comparing result that catalyzer CA, CB, CC, CD and reference agent CE, CF estimate under the same process condition.
Table 4 evaluating catalyst comparing result
| Example 7 | 8 | 9 | 10 | 11 | 12 |
| Catalyzer numbering CA | CB | CC | CD | CE | CF |
| The stock oil reaction pressure, MPa volume space velocity, h -1Hydrogen to oil volume ratio treated oil nitrogen, μ g/g | Triumph VGO 15.7 1.5 1,500 5～10 | ||||
| Temperature of reaction, oily yield in ℃ 388, w% 49.91 middle distillates oil selectivities, w% 78.51 | 386 48.44 77.90 | 387 48.59 78.25 | 392 50.35 81.50 | 391 47.23 74.12 | 389 47.17 74.31 |
From the evaluation comparing result of table 4 as can be seen, with the deep sealumination modified Y zeolite of the inventive method preparation acidic cleavage component as middle oil type hydrocracking catalyst, activity of such catalysts and middle distillates oil selectivity all are better than the evaluation result that the reference zeolite obtains under the same conditions.
Claims (8)
1, a kind of preparation method of deep sealumination modified Y zeolite may further comprise the steps:
(1) gets SiO
2/ Al
2O
3Mol ratio is 4.5～8.0, Na
2The NH of O content≤2.5w%
4The NaY zeolite is a raw material, carries out the hydrothermal treatment consists first time;
(2) zeolite that step (1) is obtained is with containing NH4
+And H
+The mixing solutions exchanging zeolite in Na
+Remove part non-framework aluminum in the zeolite simultaneously, H in the mixing solutions
+Concentration be 0.05～0.6mol/L, NH
4 +Concentration be 0.5～3.0mol/L;
(3) zeolite that step (2) is obtained carries out the hydrothermal treatment consists second time;
(4) zeolite that step (3) is obtained removes non-framework aluminum in the zeolite with acid solution.
2, in accordance with the method for claim 1, it is characterized in that the hydrothermal treatment consists temperature first time described in the step (1) is 500～700 ℃, water vapor pressure is 0.01～1.0MPa, and the treatment time is 1.0～10.0 hours.
3, in accordance with the method for claim 1, it is characterized in that the service temperature of removing part non-framework aluminum in the zeolite described in the step (2) is 70～120 ℃, the concentration of exchange slurries mesolite is 0.1～0.5g/ml, exchange and dealuminzation time are 0.5～3.0 hour, and the step of exchange and dealuminzation repeats 1～4 time.
4, in accordance with the method for claim 1, it is characterized in that the hydrothermal treatment consists temperature second time described in the step (3) is 500～800 ℃, water vapor pressure is 0.01～1.0MPa, and the treatment time is 1.0～10.0 hours.
5, in accordance with the method for claim 1, it is characterized in that for the second time the hydrothermal treatment consists temperature is higher than for the first time 10～200 ℃ of hydrothermal treatment consists temperature.
6, in accordance with the method for claim 1, it is characterized in that for the second time the hydrothermal treatment consists temperature is higher than for the first time 30～150 ℃ of hydrothermal treatment consists temperature.
7, in accordance with the method for claim 1, it is characterized in that the acid solution described in the step (4) removes the acid solution that the non-framework aluminum in the zeolite uses and is hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid or citric acid, the dealuminzation temperature is 60～120 ℃, time was generally 0.5～5 hour, acid concentration is generally 0.1～3mol/L, and the concentration of chemical dealuminization slurries mesolite is 0.05～1.0g/ml.
8, in accordance with the method for claim 1, it is characterized in that the NH described in the step (2)
4 +Derive from ammonium chloride, ammonium nitrate, volatile salt, ammonium sulfate, ammonium acetate, ammonium oxalate or ammonium citrate, H
+Derive from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid or citric acid.
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| CN101759198B (en) * | 2008-12-24 | 2011-10-12 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN102847549A (en) * | 2012-08-27 | 2013-01-02 | 王小英 | Coal tar hydrocracking catalyst and preparation method thereof |
| CN106629764A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Dealumination Y-type molecular sieve and preparation method thereof and carrier and application thereof and hydrocracking method |
| CN106629764B (en) * | 2015-10-29 | 2019-04-16 | 中国石油化工股份有限公司 | Dealuminzation Y type molecular sieve and preparation method thereof and carrier and application and catalyst and its preparation method and application and method for hydrogen cracking |
| CN108067287A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of carrier of the molecular sieve containing SBA-15 and its preparation method and application |
| CN108067287B (en) * | 2016-11-17 | 2021-04-06 | 中国石油化工股份有限公司 | Carrier containing SBA-15 molecular sieve, preparation method and application thereof |
| CN111017950A (en) * | 2019-12-31 | 2020-04-17 | 山东齐鲁华信高科有限公司 | Preparation method and application of low-cost SSZ-13 molecular sieve |
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