CN101347748B - Regeneration method of aluminum compensation for molecular sieve - Google Patents
Regeneration method of aluminum compensation for molecular sieve Download PDFInfo
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- CN101347748B CN101347748B CN200710043955A CN200710043955A CN101347748B CN 101347748 B CN101347748 B CN 101347748B CN 200710043955 A CN200710043955 A CN 200710043955A CN 200710043955 A CN200710043955 A CN 200710043955A CN 101347748 B CN101347748 B CN 101347748B
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- molecular sieve
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Abstract
The invention relates to a molecular sieve aluminum replenishment regeneration method which is mainly used for solving the problems that a regenerated catalyst of the prior art can not be repeatedly used for a long time and the regeneration process is complicated. The method counts a molecular sieve as the pure silicon molecular sieve during the regeneration process of the catalyst, uses 1 to 5 times of the needed molar ratio of silicon to aluminium to prepare aluminium salt solution with the aluminium concentration of 0.4 to 5 mol/L and carries out the contact with the catalyst, the filtration and the calcination to obtain the regenerated catalyst; therefore, the aluminum replenishment technical proposal can better solve the problems. The method can be used in the industrial production for the catalytic cracking of the naphtha to olefins.
Description
Technical field
The present invention relates to a kind of regeneration method of aluminum compensation for molecular sieve.
Background technology
Molecular sieve catalysts is applied in field of petrochemical industry widely owing to have stronger acidity, good shape selective catalysis performance and heat endurance preferably.But because framework dealumination easily takes place in the environment of high temperature or high-temperature water vapor molecular sieve catalyst, catalyst activity point loss causes inactivation, need mend aluminium and regenerate and recover activity of such catalysts.
Document (petroleum refining and chemical industry, 2004,35 (5), 15～18) reported by adding aluminium salt one-step moulding method and make and mend the aluminium beta-zeolite catalyst, the association reaction active appraisal experiment has proved that adding aluminium can make the increase of catalyst acid amount and can improve reactivity, but because in the used solution of aluminium adding moulding, because the existence of forming agent, influence the concentration and the diffusion velocity of aluminium, benefit aluminium amount is limited.
Document (SCI; 2002; 23 (10); 1930～1935) studied the influence of sodium aluminate solution processing to distribution of β zeolite sial and surface acid property; show through a series of analytical tests; the total acid content of β zeolite and strong acid amount and weak acid amount all increase, and the catalytic performance of toluene disproportionation and C9 aromatic hydrocarbons transalkylation reaction is investigated the result and shown, sodium aluminate solution is handled the selectivity of aromatics conversion rate He (benzene+toluene) that can improve beta-zeolite catalyst.But the catalyst that uses in the literary composition is the fresh catalyst of dealuminzation not, and it is limited to mend the aluminium amount, and it is comparatively complicated to mend the aluminium process.
Document (Journal of Physics Chemical B, 2000,104 (13), 2853) thinks that by to the organic citric acid treatment of β zeolite citric acid has the effect of dealuminzation and benefit aluminium simultaneously to molecular sieve.But the benefit aluminium amount that relates in the literary composition is less, does not also have the catalyst activity stability problem after aluminium is mended in explanation.
Summary of the invention
Technical problem to be solved by this invention is that the molecular sieve catalysts of prior art regeneration can not be recycled, and the regeneration technology complicated problems provides a kind of new regeneration method of aluminum compensation for molecular sieve.This method has the effect of mending aluminium, can recover the aluminum concentration of framework of molecular sieve, thereby makes the long-time advantage of using repeatedly of catalyst.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of regeneration method of aluminum compensation for molecular sieve may further comprise the steps:
(1) molecular sieve that needs to mend aluminium behind the dealuminzation being preheated temperature is 200～900 ℃;
(2) molecular sieve that needs are mended aluminium is as by SiO
2The pure silicon molecular sieve of forming is prepared the salting liquid of corresponding aluminium content concn at 0.4～5 mol aluminium with 1～5 times aluminium of required silica alumina ratio;
(3) with putting into the salting liquid of aluminium after the pre-warmed molecular sieve taking-up rapidly, filter then;
(4) filter between the good product drying, 550～900 ℃ roasting 1～10 hour, make regenerated catalyst.
In the technique scheme, described molecular sieve comprises and is selected from a kind of and coexisting molecular sieve or its mixture that contain at least two kinds of above-mentioned molecular sieves among ZSM-5, modenite, β zeolite, Y zeolite or the MCM-22.The aluminium source preferred version of used benefit aluminium is to be selected from least a in aluminate, meta-aluminate or the aluminium salt; The aluminium content concn preferable range of the salting liquid of used aluminium is 0.5～2 mol.The sintering temperature preferable range is 600～800 ℃, and the roasting time preferable range is 3～10 hours.Molecular sieve pre-heating temperature preferable range is 200～800 ℃.For obtaining better effect, can take out the catalyst after the roasting, the cooling back with the distilled water washing, filter, repeat twice after, put into oven for drying.Can repeat (1)～(4) step two to three time according to required benefit aluminium amount in addition.
The present invention puts into the way of aluminum solutions chilling then owing to adopted preheating catalyst, improved the speed that the aluminium atom diffuses into skeleton, shortened diffusion time, increased the amount of mending aluminium, roasting can be removed plane of crystal stress behind the benefit aluminium, and it is stable to help framework of molecular sieve.The remaining aluminium on water flush away surface after the roasting can make active site fully expose, and increases activity of such catalysts.Because the catalyst aluminium atom of mending after the aluminium regeneration enters framework of molecular sieve, this has increased the heat endurance of molecular sieve, again owing to the aluminium atom that enters skeleton is more, make catalyst surface acid amount bigger, acidity is stronger, thus catalytic performance is preferably arranged, and can recycle for a long time.
Adopt the catalyst after the regeneration that method of the present invention makes to can be used in the naphtha catalytic pyrolysis preparing ethylene propylene reaction, with C
4～C
10Naphtha be raw material (the raw material physical index sees Table 1), be 12 millimeters fixed bed reactors with diameter, 650 ℃, mass space velocity 0.5 hour
-1, water/oil quality is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the diene quality total recovery of ethene and propylene can reach more than 55%, has obtained better technical effect.
Table 1 feed naphtha index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.18 |
| Cycloalkane % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get and contain 60 gram silica alumina ratio SiO
2/ Al
2O
3(down with) is the catalyst of 30 ZSM-5 molecular sieve, is 1 hour at 650 ℃ with air speed
-1Steam treatment make catalyst behind the dealuminzation after 5 hours, with the oxalic acid solution washing of 0.1 mol, filter twice, put into 130 ℃ of oven dry of baking oven, with Atomic Absorption Spectrometry silica alumina ratio SiO
2/ Al
2O
3Be 85, put into Muffle furnace roasting to 500 ℃ then, put into the aluminum sulfate solution of 100 milliliter of 1 mol after the taking-up rapidly, stir after 0.5 hour, filter, put into 120 ℃ of oven dry of baking oven 2 hours then, put into Muffle furnace again, 550 ℃ of roastings 3 hours, after sample was taken out cooling, through the distilled water washed twice, drying was 3 hours under 130 ℃, promptly make the catalyst of mending behind the aluminium, with Atomic Absorption Spectrometry silica alumina ratio SiO
2/ Al
2O
3Be 62.4.
[embodiment 2～7]
The method and the content that are provided according to embodiment 1, it is as shown in table 2 to mend aluminum strip spare, mends silica alumina ratio before and after the aluminium with Atomic Absorption Spectrometry, makes the catalyst of mending behind the aluminium and sees Table 2.
Table 2
[embodiment 8]
Method according to embodiment 7 is mended aluminium, before with the distilled water washing, repeats to mend aluminium 3 times.The catalyst silica alumina ratio SiO that makes
2/ Al
2O
3Be 42.1.
[embodiment 9～11]
Get the catalyst after embodiment 2,7 and 8 mends aluminium respectively, 650 ℃, mass space velocity 0.5 per hour, water/oil quality is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the diene quality total recovery of ethene and propylene sees Table 3.
Table 3
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 9 | 27.25 | 25.68 | 52.93 |
| Embodiment 10 | 28.31 | 26.07 | 54.38 |
| Embodiment 11 | 28.45 | 27.22 | 55.67 |
[embodiment 12]
Get the catalyst that embodiment 8 makes, press the method examination of embodiment 9, begin sampling after 1 hour in reaction, after reaction is carried out 4 hours, air capacity with 400 ml/min was burnt carbon 2 hours, mended aluminium by the mode of embodiment 8 then, continued examination as stated above behind the benefit aluminium, mend aluminium regeneration 3 times continuously, appraisal result is shown in table 4 and table 5.
[comparative example 1]
Get the silica alumina ratio SiO that Shanghai petrochemical industry institute produces
2/ Al
2O
3Be 30 ZSM-5 molecular sieve, press the condition examination of embodiment 12, middlely only carry out charcoal regeneration by embodiment 12, do not mend aluminium, appraisal result is as shown in table 4.
Table 4
| Embodiment and comparative example 1 | The 1st regeneration back diene total recovery (quality %) | The 2nd regeneration back diene total recovery (quality %) | The 3rd regeneration back diene total recovery (quality %) |
| Embodiment 12 | 56.47 | 54.36 | 53.05 |
| Comparative example 1 | 52.35 | 50.31 | 47.89 |
Table 5
| Embodiment 12 | React diene total recovery (quality %) after 1 hour | React diene total recovery (quality %) after 3 hours |
| Before mending aluminium regeneration | 57.60 | 52.26 |
| After mending aluminium regeneration | 56.45 | 51.08 |
Claims (6)
1. regeneration method of aluminum compensation for molecular sieve may further comprise the steps:
(1) molecular sieve that needs to mend aluminium behind the dealuminzation being preheated temperature is 200～900 ℃;
(2) molecular sieve that needs are mended aluminium is as by SiO
2The pure silicon molecular sieve of forming is prepared the salting liquid of corresponding aluminium content concn at 0.4～5 mol aluminium with 1～5 times aluminium of required silica alumina ratio;
(3) with putting into the salting liquid of aluminium after the pre-warmed molecular sieve taking-up rapidly, filter then;
(4) filter between the good product drying, 550～900 ℃ roasting 1～10 hour, make regenerated catalyst.
2. regeneration method of aluminum compensation for molecular sieve according to claim 1 is characterized in that molecular sieve comprises to be selected from a kind of and coexisting molecular sieve or its mixture that contain at least two kinds of above-mentioned molecular sieves among ZSM-5, modenite, β zeolite, Y zeolite or the MCM-22.
3. regeneration method of aluminum compensation for molecular sieve according to claim 1, the aluminium source that it is characterized in that mending aluminium are selected from least a in aluminate, meta-aluminate or the aluminium salt.
4. regeneration method of aluminum compensation for molecular sieve according to claim 1, the aluminium content concn that it is characterized in that the salting liquid of aluminium is 0.5～2 mol.
5. regeneration method of aluminum compensation for molecular sieve according to claim 1 is characterized in that the molecular sieve pre-heating temperature is 200～800 ℃.
6. regeneration method of aluminum compensation for molecular sieve according to claim 1 is characterized in that described sintering temperature is 600～800 ℃, and roasting time is 3～10 hours.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962094A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院大连化学物理研究所 | Method for improving acidity of MCM-22 molecular sieve based catalyst |
| CN104549438B (en) * | 2013-10-18 | 2017-04-26 | 中国石油化工股份有限公司 | Framework aluminum supplementing method of molecular sieve based catalyst |
| CN104556102B (en) * | 2013-10-28 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of preparation method of low silica-alumina ratio molecular sieve |
| CN105294373B (en) * | 2014-05-30 | 2017-03-22 | 中国石油化工股份有限公司 | Separation method for aqueous organic matter |
| CN108855021B (en) * | 2018-06-29 | 2021-05-14 | 万华化学集团股份有限公司 | 13X molecular sieve activation regeneration method |
| CN111252783A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Low silicon-aluminum ratio MFI type molecular sieve synthesis method |
| CN111229293A (en) * | 2019-11-20 | 2020-06-05 | 复榆(张家港)新材料科技有限公司 | Zeolite molecular sieve catalyst for preparing hydrocarbons by methanol dehydration and preparation method thereof |
| CN113289679B (en) * | 2021-06-24 | 2023-09-26 | 陕西延长石油（集团）有限责任公司 | Method for regenerating waste catalyst framework containing molecular sieve by supplementing aluminum and reactivating |
| CN113426494A (en) * | 2021-06-24 | 2021-09-24 | 陕西延长石油（集团）有限责任公司 | Method for reactivating and regenerating waste catalytic cracking catalyst |
| CN115608412B (en) * | 2022-09-30 | 2024-04-05 | 陕西延长石油（集团）有限责任公司 | Method for regenerating catalyst containing molecular sieve by supplementing aluminum |
| CN115608413A (en) * | 2022-10-12 | 2023-01-17 | 陕西延长石油（集团）有限责任公司 | Gas phase aluminum supplement regeneration method for molecular sieve-containing catalyst |
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| US5620935A (en) * | 1995-08-01 | 1997-04-15 | Degussa Aktiengesellschaft | Method for the regeneration of a catalyst |
| CN1277893A (en) * | 2000-07-05 | 2000-12-27 | 复旦大学 | Method for preparing modified beta zeolite catalyst used for alkylation reaction of isobutane/butylene |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620935A (en) * | 1995-08-01 | 1997-04-15 | Degussa Aktiengesellschaft | Method for the regeneration of a catalyst |
| CN1277893A (en) * | 2000-07-05 | 2000-12-27 | 复旦大学 | Method for preparing modified beta zeolite catalyst used for alkylation reaction of isobutane/butylene |
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