CN1291917C - Method for synthesizing Y-zeolite composite material - Google Patents
Method for synthesizing Y-zeolite composite material Download PDFInfo
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- CN1291917C CN1291917C CN 200410048098 CN200410048098A CN1291917C CN 1291917 C CN1291917 C CN 1291917C CN 200410048098 CN200410048098 CN 200410048098 CN 200410048098 A CN200410048098 A CN 200410048098A CN 1291917 C CN1291917 C CN 1291917C
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Abstract
The present invention discloses a method for synthesizing Y-type zeolite composite material, which comprises the following steps that kaolin is converted into meta-kaolin through calcination and dehydration at the temperature from 500 to 900 DEG C, and the meta-kaolin is made into powder of which the particle diameter is smaller than 230 micron through crushing; sodium silicate, guide agent, sodium hydroxide and water are added to the powder, and mother liquid is crystallized, filtered and collected; the collected mother liquid can be directly recycled; and the collected mother liquid performs the functions of partial or total sodium silicate and sodium hydroxide to be utilized.
Description
Technical field
The invention relates to a kind of synthetic method of Zeolite composite materials, more specifically say so about a kind of method by the synthetic y-type zeolite matrix material of kaolin in-situ crystallization.
Background technology
Y-type zeolite is a petroleum catalytic cracking activity of such catalysts constituent element.Gel directing agent method and kaolin microsphere in-situ crystallization method are two kinds of main technique methods of present industrial production y-type zeolite.
USP3 discloses the method for the synthetic y-type zeolite of gel directing agent method in 639,099 and USP4,166,099.In gel directing agent method synthesis technique, the subject matter of existence is that the silica alumina ratio in feeding intake is higher, and the utilization ratio of silicon is low, has only 51-54% (Li Zhong county etc., refining of petroleum and chemical industry, 1998, V29 (10), 24～26), SiO in the crystallization synthesis mother liquid
2Content be 50～55g/L, Na
2O content be 20～25g/L (open prizes pool etc., petrochemical technology, 2002,9 (2): 83～86), a large amount of SiO in feeding intake like this
2Be discharged with mother liquor Deng active principle, strengthened the waste of consumption of raw materials and resource, increased the cost of product; Needed follow-up sewage treatment process to handle by row's mother liquor sewage, the mother liquid recovery process of domestic general employing is to add a certain amount of alum liquor in crystallization mother liquor, with the precipitation of the silicon in the mother liquor, then after filtration, washing preparation alumino silica gel.If the Na in the crystallization mother liquor
2The O height, also brought certain degree of difficulty for the filter residue comprehensive treating process, cause the filter residue processing costs to increase and environment has also been caused bigger pollution, in case the filter residue amount is too many, the way of escape that causes filter residue to handle is stopped up, to have a strong impact on the ordinary production of whole catalyst plant again, and cause pollution also for local environment.
USP4, the kaolin microsphere in-situ crystallization method that proposes in 493,902.USP3,506,594, USP3,503,900, USP3,647,718 to have proposed be the in-situ crystallization technology that raw material prepares active ingredient and matrix simultaneously with kaolin, above technology and patent USP3,377,886, USP3,367,887, USP3,657,154, USP3,663,165, USP3,932, the problem that methods such as 268T exist is: 1) product degree of crystallinity is low, and NaY content is less than 30%; 2) maturing temperature height substantially all adopts the kaolin of roasting more than 900 ℃, and energy consumption is big; 3) a large amount of SiO in synthetic the feeding intake
2Be discharged with mother liquor Deng active principle.
The disclosed technology employing of USP4493902 is carried out the high and low temperature roasting respectively with kaolin and is prepared microballoon, and its degree of crystallinity obtains bigger raising, reaches 70%.But its raw material is a super-refinement kaolin, costs an arm and a leg, market is difficult to buy, in addition, and its liquid phase SiO
2The ratio of/microballoon kaolin weight is greater than 1.9, and the silica alumina ratio in synthetic the feeding intake is higher, and the utilization ratio of silicon is low; The ratio of water/microballoon weight is greater than 4.9, and the output of mother liquor is also bigger.Though, also once adopted in this technology and filtered back mother liquor replacement portion water glass after concentrating, be used to synthesize, but because the output of mother liquor is bigger, the workload of concentration technology is also bigger, and relatively large invalid water glass circulates in technology, and itself has just increased production cost.
CN1232862 adopts the similar technology of USP4493902, and degree of crystallinity is less, and NaY content is less than 40%.
The problem that NaY content among the CN1232862 is little in order to solve for CN1334142A, active ingredient and matrix can't be adjusted proposes to adopt the scheme of the former powder of kaolin, its liquid phase SiO
2The ratio of/(high soil+native partially) weight drops to 0.4-2.0.From embodiment, as liquid phase SiO
2The weight ratio of/(high soil+soil) partially than hour, have the problem that degree of crystallinity is low or the product silica alumina ratio is low, this will produce a very large impact the thermostability of product; In addition, this method adopts two kinds of temperature roasting kaolins, has increased the complicated process of preparation degree, and the requirement of roasting apparatus has also been improved, because the minimum maturing temperature of kaolin is 730 ℃, its energy consumption is also bigger.Adopt among the embodiment of single metakaolin liquid phase SiO in this patent
2The ratio of/(high soil+native partially) weight is much larger than 2.
Summary of the invention
It is low to the purpose of this invention is to provide a kind of cost, the synthetic method of environment amenable y-type zeolite matrix material.
The inventor finds, by the reduction silica alumina ratio that feeds intake, maximized utilize the silicon source in the water glass and feed intake in Na
2O on the basis that obtains the satisfied product of silica alumina ratio, reduces SiO in the crystallization mother liquor greatly
2And Na
2The content of O; Again crystallization mother liquor is not dealt with, return in the synthetic system, can realize that molecular sieve cleans the technique of zero discharge target of production as part of raw materials.
Therefore, the synthetic method of y-type zeolite matrix material provided by the invention comprises the steps:
(1) kaolin is changed into metakaolin in 500～690 ℃ of roastings dehydration, pulverize and make particle diameter less than 230 microns powder;
(2) the metakaolin powder is mixed with water glass, directed agents, sodium hydroxide solution and water, make proportioning and be (1～2.5) Na
2O: Al
2O
3: (4～9) SiO
2: (40～100) H
2The reaction raw materials of O, wherein, the weight ratio of directed agents and metakaolin is 0.1～1.0,
(3) reaction raw materials that step (2) is made is at 88～98 ℃ of dynamic crystallizations, and filtering also then, drying obtains product;
(4) mother liquor after the crystallization filtration is collected, directly returned and substitute all or part of water glass and sodium hydroxide recycling in the step (2).
In the method provided by the invention, said kaolin is selected from hard kaolin or soft kaolin; Its crystalline content should be preferably greater than 85 heavy % greater than 75 heavy %, and its median size is less than 4 microns, so be the original soil without forming processes.
In the method provided by the invention, said kaolin also can be to handle the kaolin that obtains through peracid or alkali or salt, said acid can be mineral acid and organic acids such as hydrochloric acid, nitric acid, acetate, oxalic acid, oxalic acid, sulfuric acid, phosphoric acid, wherein preferred hydrochloric acid and nitric acid; Said alkali can be sodium hydroxide, potassium hydroxide, ammoniacal liquor etc., wherein preferred sodium hydroxide; Said salt is selected from yellow soda ash or sodium bicarbonate.
Described kaolinic maturing temperature is 500～900 ℃, preferred 500～700 ℃, and more preferably 640～680 ℃, general roasting time is 1～10 hour.
In the method provided by the invention, the used directed agents of step (2) can be synthetic according to the method for routine, as according to USP3574538, and 3639099, USP3671191, USP4166099, the preparation method of EUP0435625 is synthetic.Consisting of of directed agents: (10-17) SiO
2: (0.7-1.3) Al
2O
3: (11-18) Na
2O: (200-350) H
2O, preferably wearing out under 4～20 ℃ obtains.
In the method provided by the invention, the used filter type of step (4) can be centrifugation, band filter etc., and mother liquor can be the first-time filtrate of centrifugation, also can be the mixing solutions of first-time filtrate and follow-up scavenging solution.Method provided by the invention, the silica concentration of synthesis mother liquid is not more than 9 heavy %, sodium oxide concentration is not more than 3 heavy %, alumina concentration is not more than 0.5g/L, mother liquor need not be handled, directly can be used as reaction raw materials, the effect of all or part of alternative water glass and sodium hydroxide is used for the synthetic of y-type zeolite matrix material.Said crystallization steps is carried out under the dynamic agitation situation in the method provided by the invention, and for example, the crystallization stirring velocity is 200～1000 rev/mins, and preferred 400～600 rev/mins, the time is 16～48 hours, preferred 24～32 hours.
Synthetic method provided by the invention, its synthesis mother liquid can be used for the synthetic of Y zeolite matrix material without the direct instead of part raw material of any processing, has following advantage:
(1) directly utilizes synthesis mother liquid, greatly reduce the sewage disposal expense.
(2) this synthetic method has that the silica alumina ratio of feeding intake is low, the water aluminum ratio is low, product silica alumina ratio height, and the characteristics that single-autoclave yield rate is high, the thermostability and the hydrothermal stability of product are good.
Embodiment
The invention will be further described below by embodiment, but content not thereby limiting the invention.
Among the embodiment in the matrix material content of NaY zeolite measure according to the RIPP146-90 standard method that (" petrochemical complex analytical procedure (RIPP test method) " seen in the RIPP standard method, Yang Cui waits volume surely, Science Press, and nineteen ninety publishes, draw by relative crystallinity down together).
Lattice constant a
0Measure according to the RIPP145-90 standard method.
RE
2O
3Content measure according to the RIPP131-90 standard method.
The silica alumina ratio of NaY zeolite is by lattice constant a
0, calculate according to following formula:
SiO
2/ Al
2O
3(mol ratio)=2 * (25.858-a
0)/(a
0-24.191)
NaY zeolite specific surface is measured according to nitrogen adsorption method (GB/T5816-1995), and pore volume is measured according to nitrogen adsorption method (RIPP151-90), and zeolite avalanche temperature is measured according to differential thermal analysis (DTA) method.
Embodiment 1
The preparation of directed agents: get the 250 gram sodium silicate solution (SiO that contain 20.05 heavy %
2, 6.41 heavy % Na
2O), 30 ℃ are stirred down the slowly adding 120 gram sodium aluminate solution (Al that contain 3.15 heavy % fast
2O
3, the Na of 21.1 heavy %
2O), stirred 1 hour, 20 ℃ were worn out 48 hours, and obtained directed agents.Directed agents consists of 16Na
2O: Al
2O
3: 15 SiO
2: 320 H
2O.
With median size is the kaolin (China Kaolin Co., Ltd, crystalline content is 80 heavy % for Suzhou, Yangshan board) of 4 μ m, 660 ℃ of roastings 3 hours, obtains the metakaolin powder, pulverizes and makes the metakaolin powder of particle diameter less than 230 μ m.
Get 100 kilograms of metakaolin powder after the pulverizing, stir 400 kilograms of sodium silicate solutions of adding (SiO that contains 20.05 heavy % down
2, the Na of 6.41 heavy %
2O), the directed agents of 60 kilograms (1) step preparation, 100 kilograms of concentration are the sodium hydroxide solution of 5 heavy %.Be warming up to 90 ℃ of constant temperature and stirred crystallization 28 hours, mixing speed is 400 rev/mins when feeding in raw material with crystallization.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with crystallization jar chilling.120 ℃ of dryings 2 hours obtain zeolite Y-1.NaY content is 38.9 heavy % among the X-ray diffraction mensuration Y-1, and lattice constant is 24.65.
Mother liquor reclaims: mother liquor is reclaimed storage, obtain mother liquor M-1.Its concentration is SiO
22.0%, Na
2O0.72%, Al
2O
30.5g/L.
Embodiment 2
Press the method for embodiment 1, different was with feed kaolin 680 ℃ of roastings 4 hours, and mixing speed is 600 rev/mins during the reaction raw materials crystallization, and gained y-type zeolite matrix material is numbered Y-2.
Measure through X-ray diffraction, NaY content is 52.4 heavy % among the Y-2, and its physical and chemical performance sees Table 1.
Mother liquor is reclaimed storage, obtain mother liquor M-2.Its concentration is SiO
25.0%, Na
2O1.72%, Al
2O
30.5g/L.
Embodiment 3
Press the method for embodiment 1, making proportion of raw materials is 2.2Na
2O: Al
2O
3: 8.4SiO
2: 80.2H
2O, gained y-type zeolite matrix material is numbered Y-3.
NaY content is 32.8 heavy % among the Y-3, and lattice constant is 24.68.
Mother liquor is reclaimed storage, obtain mother liquor M-3.Its concentration is SiO
27.0%, Na
2O2.70%, Al
2O
30.5g/L.
Embodiment 4
Press the method for embodiment 1, different is that mother liquor M-1 is all replaced sodium hydroxide solution, adds 2 kilograms of sodium hydroxide again, and crystallization time is 29 hours, and gained y-type zeolite matrix material is numbered Y-4.
NaY content is 59.6 heavy % among the Y-4, and lattice constant is 24.65, and physico-chemical property sees Table 1.
Embodiment 5
Press the method for embodiment 1, different is that mother liquor M-2 is all replaced sodium hydroxide solution, adds 2 kilograms of sodium hydroxide again, and crystallization time is 29 hours, and gained y-type zeolite matrix material is numbered Y-5.
NaY content is 69.6 heavy % among the Y-5, and lattice constant is 24.64, and physico-chemical property sees Table 1.
Embodiment 6
With the method for embodiment 1, different is that mother liquor M-3 is all replaced sodium hydroxide solution, adds 2 kilograms of sodium hydroxide again, the sodium silicate solution (SiO that contains 20.05 heavy %
2, the Na of 6.41 heavy %
2O) add-on is 360 kilograms, and crystallization time is 29 hours, and gained y-type zeolite matrix material is numbered Y-6.
NaY content is 60.6 heavy % among the Y-6, and lattice constant is 24.65, and physico-chemical property sees Table 1.
Embodiment 7
Press the method for embodiment 4, the kaolin powder that different is adds is that 2 hydrochloric acid soln is handled 2h at 70 ℃ through pH value, stirring crystallization 29h, and gained y-type zeolite matrix material is numbered Y-7.
NaY content is 63.3 heavy % among the Y-7, and lattice constant is 24.68.
Embodiment 8
Press the method for embodiment 4, different is, and the kaolin powder through pH value is that 14 sodium hydroxide solution is handled 2h at 70 ℃, do not need to add sodium hydroxide in the mother liquor again, stirring crystallization 29h, and gained y-type zeolite matrix material is numbered Y-8.
NaY content is 75.0 heavy % among the Y-8, and lattice constant is 24.68.
Table 1
| The zeolite numbering | Y-2 | Y-4 | Y-5 | Y-6 |
| NaY content, heavy % | 52.4 | 59.6 | 69.6 | 60.6 |
| Silica, mol ratio | 5.2 | 5.2 | 5.4 | 5.2 |
| Lattice constant, | 24.65 | 24.65 | 24.64 | 24.65 |
| Specific surface area, m 2/g | 470.5 | 528.3 | 600.3 | 540.0 |
| The BET total pore volume, ml/g | 0.22 | 0.25 | 0.37 | 0.34 |
| The structural breakdown temperature, ℃ | 896 | 912 | 917 | 914.8 |
Embodiment 9
Present embodiment illustrates the catalytic activity and the stability of y-type zeolite matrix material provided by the invention.
At first with the matrix material rare earth exchanged of embodiment 2,4,5,6,7 preparation: get 100 gram matrix materials, add 100 and restrain NH
4Cl and 1000 gram deionized waters, 90 ℃ were stirred 2 hours, washing, filtered, and 120 ℃ of dryings 2 hours obtain NH
4Y zeolite; Get 100 gram NH
4Y zeolite is pressed NH
4Y: REO: H
2O is 1: 0.1: 10 a ratio, adds deionized water, is 4.5 with dilute hydrochloric acid regulator solution pH value, adds mixed chlorinated rare earth solution again, and 90 ℃ are stirred exchange and carried out ion-exchange 2 hours, wash, after the filtration, with the solid collected 560 ℃ of roastings 2 hours.Again roasting material is pressed REY: NH
4Cl: H
2O=1: 0.3: 10 ratio feeds intake, and carries out ammonium exchange 1 hour under 90 ℃ of following agitation conditions, washing, filters, and 120 ℃ of dryings 2 hours repeat ammonium exchange once by this condition again, obtain the REY zeolite of sodium oxide content less than the rare earth exchanged of 0.3 weight %.Numbering, content of rare earth and the numbering of the y-type zeolite matrix material of the REY zeolite correspondence that obtains see Table 2.
Table 2
| Raw material zeolite numbering | Y-2 | Y-4 | Y-5 | Y-6 | Y-7 |
| REY numbers Na 2O REO SiO 2 Al 2O 3 | REY-1 0.12 11.5 65 25 | REY-2 0.10 10.7 58.4 23.0 | REY-3 0.13 9.3 65 24 | REY-4 0.16 9.1 63 23 | REY-5 0.13 9.2 65 24 |
With each REY 810 ℃ with 100% water vapour aging 8 hours and 17 hours, drying then is that 239～351 ℃ light oil carries out micro anti-evaluation to its catalytic performance with boiling range, the results are shown in Table 3.
Table 3
As shown in Table 3, the zeolite of the present invention's preparation still has hydrothermal stability preferably after the harsh burin-in process of process, and it is higher to show as micro-activity, illustrates through present method synthetic Y zeolite matrix material to have good hydrothermal stability.
Claims (13)
1. the synthetic method of a y-type zeolite matrix material is characterized in that this method comprises the steps:
(1) kaolin is changed into metakaolin in the dehydration of 500～900 ℃ of roasting temperatures, pulverize and be the powder of particle diameter less than 230 microns;
(2), make proportioning and be (1～2.5) Na with metakaolin and water glass, directed agents, sodium hydroxide solution and water
2O: Al
2O
3: (4～9) SiO
2: (40～100) H
2The reaction raw materials of O, wherein the weight ratio of directed agents and metakaolin is 0.1～1.0;
(3) reaction raw materials crystallization under 88～98 ℃ of stirrings that (2) step is made is filtered then and drying obtains product;
(4) mother liquor after the crystallization filtration is collected, directly returned and substitute all or part of water glass and sodium hydroxide recycling in the step (2).
2. according to the method for claim 1, said kaolin is selected from hard kaolin or soft kaolin.
3. according to the method for claim 2, crystalline content is greater than 75 heavy % in the said kaolin.
4. according to the method for claim 3, crystalline content is greater than 85 heavy % in the said kaolin.
5. according to method arbitrary in the claim 1～4, said kaolin is for handling the kaolin that obtains through peracid or alkali or salt, said acid is selected from a kind of or its mixture in hydrochloric acid, nitric acid, acetate, oxalic acid, oxalic acid, sulfuric acid, the phosphoric acid, said alkali is selected from a kind of or its mixture in sodium hydroxide, potassium hydroxide, the ammoniacal liquor, and said salt is selected from yellow soda ash or sodium bicarbonate.
6. according to the method for claim 5, said acid is hydrochloric acid or nitric acid.
7. according to the method for claim 5, said alkali is sodium hydroxide.
8. according to the method for claim 1, kaolinic maturing temperature is 500～700 ℃ in the step (1).
9. according to the method for claim 8, said maturing temperature is 640～680 ℃.
10. according to the method for claim 1, said directed agents consists of: (10-17) SiO
2: (0.7-1.3) Al
2O
3: (11-18) Na
2O: (200-350) H
2O.
11. according to the method for claim 1 or 10, said directed agents obtains for wearing out under 4～20 ℃.
12. according to the method for claim 1, said mother liquor is for separating the first-time filtrate behind the synthetic product or the mixing solutions of first-time filtrate and follow-up scavenging solution.
13. according to the method for claim 12, silica concentration is not more than 9 heavy % in the said mother liquor, sodium oxide concentration is not more than 3 heavy %, and alumina concentration is not more than 0.5g/L.
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| CN101746778B (en) * | 2008-11-28 | 2012-08-29 | 中国石油化工股份有限公司 | Composite material containing double-pore structure Y-type zeolite, and preparation method thereof |
| CN102050466B (en) * | 2009-10-27 | 2012-08-29 | 中国石油化工股份有限公司 | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material |
| CN104340990B (en) * | 2013-07-31 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of synthetic method of y-type zeolite |
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN105417553B (en) * | 2014-09-17 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of NaY molecular sieve and preparation method thereof |
| CN105645433B (en) * | 2016-03-29 | 2017-12-12 | 东北大学 | A kind of method for synthesizing Y type molecular sieve with kaolin dynamic |
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| CN114534774A (en) * | 2020-11-25 | 2022-05-27 | 中国石油化工股份有限公司 | Composite material, catalytic cracking catalyst and preparation method thereof |
| US20230249165A1 (en) * | 2020-06-23 | 2023-08-10 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst and process for preparing the same |
| CN114471693A (en) * | 2020-11-13 | 2022-05-13 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalyst and preparation method thereof |
| CN113828350A (en) * | 2020-06-23 | 2021-12-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN114425429A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Wear-resistant high-yield low-carbon olefin catalyst and preparation method thereof |
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