CN104230633A - Liquid phase alkyl transfer method - Google Patents
Liquid phase alkyl transfer method Download PDFInfo
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- CN104230633A CN104230633A CN201310236993.8A CN201310236993A CN104230633A CN 104230633 A CN104230633 A CN 104230633A CN 201310236993 A CN201310236993 A CN 201310236993A CN 104230633 A CN104230633 A CN 104230633A
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Abstract
The invention relates to a liquid phase alkyl transfer method, and mainly solves the problems of low utilization rate of catalyst, low reaction activity, andpoor strength and stability of catalyst when a catalyst containing binder is used in the prior art. The invention adopts multi-ethyl benzene and benzene as the raw materials, and raw materials contact with a catalyst to generate a liquid alkyl transfer reaction under the conditions of reaction temperature of 100-260 DEG C, reaction pressure of 2.0-4.5 MPa, liquid phase weight space velocity of 1-10 / h and weight ratio of benzene / ethyl benzene of 1-10; the catalyst is a binder-free Y-type molecular sieve with SiO2 / Al2O3 ratio of 3-20. The technical scheme well solves the above problems, and can be used in industrial production of ethylbenzene through multi ethyl benzene and benzene liquid phase alkyl transfer.
Description
Technical field
The present invention relates to a kind of liquid phase transfer method.
Background technology
Ethylbenzene is important Organic Chemicals, and industrial main being used as produces cinnamic raw material.Ethylbenzene is obtained by alkylated reaction primarily of benzene and ethene, and its alkylation process is generally divided into gas molecule in space sieve method and liquid phase molecule sieve method.It is no matter the alkylation process of gas molecule in space sieve method or liquid phase molecule sieve method, because reaction product ethylbenzene can equally with benzene feedstock continue to generate many ethylbenzene components such as diethylbenzene, triethyl-benzene, four ethylbenzene with ethene generation alkylated reaction, so all establish independently transalkylation reactor in the ethylbenzene industrial production in modern times, after many ethylbenzene material that this part is separated from alkylation reaction product and benzene mixing, generate ethylbenzene by transalkylation catalyst reaction.Do the generation that not only can reduce side reaction in alkylated reaction like this, improve the life-span of alkylation catalyst, also can improve the productive rate of ethylbenzene.
What early stage patent US3751504, US4016218, US3962364 and CN1310051 selected is vapor-phase transalkylation technique, the catalyst activity component adopted is ZSM-5 molecular sieve, have employed unmodified HZSM-5, the HZSM-5 molecular sieve of steam-treated, element phosphor modification and steam-treated respectively and is aided with the HZSM-5 molecular sieve of organic acid process modification.This makes the performance of gas phase alkyl catalyst obtain significantly to improve.But the strength of acid that transalkylation reaction needs is higher than alkylated reaction, simultaneously in order under keeping reaction mass to be in gas phase condition, vapor-phase transalkylation reaction all needs very high temperature of reaction, is generally greater than 400 DEG C.The side reaction which results in vapor-phase transalkylation reaction is many, and the comparision contents of dimethylbenzene and impurity is high, and catalyst life is shorter.Meanwhile, in order to maintain high selectivity, the transformation efficiency of vapor-phase transalkylation is all lower, and most high maintenance is 60%.
Along with advantage studied personnel's understanding gradually of liquid phase method low-temp reaction, the method for molecular sieve liquid phase transfer is developed successively.US4774377 discloses a kind of liquid phase transfer process, and adopt the reactor of upper entering and lower leaving, bottom in and top out or horizontal positioned, its catalyzer can adopt X, Y type, L-type, USY, omega zeolite and mordenite, recommends to adopt mordenite.Patent US3551510 disclosed a kind of product by being separated gas phase alkylation process, obtains product ethylbenzene, isolated many ethylbenzene and benzene is carried out separately the technique of reacting with a top-down transalkylation reactor simultaneously, liquid air speed 1.0 hours
-1, temperature 250 DEG C, under pressure 3.4MPa condition, adopt mordenite use as transalkylation catalyst.Adopt mordenite temperature of reaction higher in these patents, material air speed is also lower simultaneously, and described catalyzer all for there being the molecular sieve of binding agent, causes catalyst utilization lower.
CA2022982 describes the technological process of concrete liquid phase transfer, adopts y-type zeolite to use as transalkylation catalyst.US4169111 describes in detail and adopts independent transalkylation process from bottom to top, recommends to adopt Na
2o content 0.2%, the Y molecular sieve of water vapor super stabilizing process uses as transalkylation catalyst.Be recommended in temperature 232 ~ 343 DEG C, pressure 2.8 ~ 6.9MPa, total quality of material air speed was at 2 ~ 10 hours
-1, benzene and diethylbenzene mol ratio are reacted under 2 ~ 5 conditions.Can find out in this patent that after adopting the Y molecular sieve of water vapor super stabilizing process to do transalkylation catalyst, material air speed increases, but temperature of reaction is still higher.Japanese Patent JP1135728 discloses the preparation method of diethylbenzene and benzene transalkylation catalyst under a kind of liquid-phase condition, adopts the Y zeolite of ferro element modification, but this catalyzer is with containing H before the reaction
2and H
2the gas of S carries out pre-treatment, the preprocessing process more complicated before catalyzer uses.CN1323739A describes a kind of Y zeolite for many ethylbenzene and benzene liquid phase transfer process, prepared molecular sieve is by DEG C process 0.5 ~ 4 hour in room temperature ~ 650 under ammonia atmosphere of at least one step, and preferably 150 ~ 600 DEG C process the step of 1 ~ 3 hour and obtain.CN1359752A describes a kind of for the catalyzer by polyalkylbenzene and benzene manufacture order alkylbenzene, by SiO
2/ Al
2o
3mol ratio is HY zeolite and the inert component formation of 8 ~ 20, wherein Y zeolite weight range is 40 ~ 90%, and all the other are one or more the auxiliary element being selected from P, alkali and alkaline earth metal ions element of inert component and 0.01 ~ 5% (weight).This catalyzer is used for multi-ethyl phenenyl and benzene liquid phase transfer process produces ethylbenzene, and the transformation efficiency of multi-ethyl phenenyl is greater than 60%, and the selectivity generating ethylbenzene is greater than 99%, xylene content < 120ppm in ethylbenzene.CN1373006A describes a kind of catalyzer for being produced ethylbenzene by multi-ethyl phenenyl and benzene, by SiO
2/ Al
2o
3mol ratio is Y zeolite and the inert formation of 8 ~ 20, and wherein Y zeolite weight range is 40 ~ 90%, and all the other are inert.The sour feature of this catalyzer is the ratio at middle strong acid center (330 ~ 600 DEG C of ammonia desorption relative acid centers) and weak acid center (150 ~ 330 DEG C of ammonia desorption relative acid centers) is 65: 35 ~ 35: 65.This catalyzer is used for multi-ethyl phenenyl and benzene liquid phase transfer process produces ethylbenzene, and the transformation efficiency of multi-ethyl phenenyl is greater than 70%, and the selectivity generating ethylbenzene is more than or equal to 98%.The common ground of above-mentioned patent all refer to the modification research to Y zeolite, but the Y zeolite adopted is all shaping with the binding agent such as silicon oxide or aluminum oxide, wherein the content of inert component binding agent is mostly greater than 20%, when in the liquid phase shift reaction for multi-ethyl phenenyl and benzene, catalyst activity component utilization ratio is low, and the loadings of catalyzer is larger.Simultaneously due to binding agent wrapping portion molecular sieve, plug the duct of moieties sieve active ingredient, diffusion is deteriorated.
Summary of the invention
Technical problem to be solved by this invention is that prior art existence adopts containing catalyst utilization during binder catalyst low, and reactive behavior is low, and catalyst strength is poor, the problem of poor stability, provides a kind of new liquid phase transfer method.It is high that the method has reactive behavior, the feature that catalyst stability is good, intensity is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of liquid phase transfer, with multi-ethyl phenenyl and benzene for reaction raw materials, temperature of reaction 100 ~ 260 DEG C, and reaction pressure 2.0 ~ 4.5MPa, liquid phase weight air speed 1 ~ 10 hour
-1, under the condition of benzene/multi-ethyl phenenyl weight ratio 1 ~ 10, reaction raw materials and catalyst exposure generation liquid phase shift reaction generate ethylbenzene; Wherein, described catalyzer is SiO
2/ Al
2o
3mol ratio is the binder free Y zeolite of 3 ~ 20.
In technique scheme, preferably, in described binder free Y zeolite, the content of molecular sieve is greater than 95 % by weight.
In technique scheme, preferably, described binder free Y zeolite SiO
2/ Al
2o
3mol ratio is 5 ~ 15.
In technique scheme, preferably, described binder free Y zeolite is through steam-treated.Steam-treated temperature is 400 ~ 800 DEG C, and the treatment time is 0.5 ~ 24 hour, and the weight space velocity of water vapour is 1 ~ 10 hour
-1.
In technique scheme, preferably, temperature of reaction is 150 ~ 240 DEG C.
In technique scheme, preferably, reaction pressure is 2.5 ~ 4.0MPa.
In technique scheme, preferably, liquid phase weight air speed is 1 ~ 5 hour
-1.
In technique scheme, preferably, benzene/multi-ethyl phenenyl weight ratio is 1 ~ 5.
In technique scheme, preferably, the many ethylbenzene of raw material is pure ethylene method, rare ethylene process or alcohol legal system be for the many ethylbenzene produced in ethylbenzene.
Binder free Y zeolite in the inventive method is by SiO
2/ Al
2o
3mol ratio be the former powder of Y zeolite of 3 ~ 20 according to the alkaline matter of butt weight 20 ~ 80% and 0.1 ~ 15%, the compound of aluminium of 0.1 ~ 10% and the compound of the silicon of 10 ~ 80%, grind shaping, extrusion, dries, and obtains after roasting through aftertreatment again.Wherein, described alkaline matter is selected from sodium hydroxide, and the compound of aluminium is selected from sodium metaaluminate, and the compound of silicon is selected from silicon-dioxide.The optimum ratio of raw material is: the former powder of Y zeolite according to the alkaline matter of butt weight 50 ~ 60% and 0.5 ~ 5%, the compound of aluminium of 1 ~ 5 and the compound of the silicon of 40 ~ 60%.
Above-mentioned post-processing step comprises:
A, is placed in Autoclaves for synthesis by above-mentioned strip catalyst, and synthesis reactor bottom loads deionized water, catalyzer is placed on stainless (steel) wire, and ensures that catalyzer does not contact with the water of autoclave base, sealing autoclave.Static crystallization 5 ~ 200 hours at 90 ~ 200 DEG C of temperature, opens the catalyzer after still taking-up crystallization.Wherein, the optimum condition of crystallization is: 100 ~ 180 DEG C, crystallization 10 ~ 30 hours.
B, the catalyzer deionized water wash taken out by step a at least one times, is dried, roasting.
C, carries out conventional ammonium ion exchange at least one times, preferably four times by above-mentioned Adhesive-free Molecular Sieve; Steam roasting process.
D, repeating step c once, namely obtain the binder free Y zeolite after crystallization.
In above-mentioned steps, bake out temperature is 100 ~ 150 DEG C, and drying time is 1 ~ 10 hour; Maturing temperature is 400 ~ 600 DEG C, and roasting time is 1 ~ 10 hour.
In the inventive method, ammonium ion exchange treatment process is the conventional method adopted in prior art, and the present invention has no particular limits it.Such as use the ammonium salt solution of weight concentration 1 ~ 20%, under 0 ~ 100 DEG C of condition, process 0.5 ~ 24 hour.Described ammonium salt is selected from least one in ammonium nitrate, ammonium chloride, ammonium oxalate, ammonium sulfate or ammonium citrate.Described exchange generally also comprises filtration, water-washing step.In the present invention, steam roasting treatment process is the conventional method adopted in prior art, and the present invention has no particular limits it.Such as at 400 ~ 800 DEG C, under containing the water vapour atmosphere of 10 ~ 100%, carry out steam roasting process 0.5 ~ 24 hour.
The inventive method can be used for the liquid phase transfer process of many ethylbenzene component and the benzene produced by the rare ethylbenzene manufactured from ethylene alkylation process in ethene or catalytic cracked dry gas, also can be used for the liquid phase transfer process of many ethylbenzene component and the benzene produced by alcohol legal system ethylbenzene alkylation process.
The inventive method adopts binder free Y zeolite as liquid phase transfer catalyst, binder free Y zeolite adds the content of wherein Y zeolite, eliminating binding agent parcel, to cover the activity brought of active ingredient low, the unfavorable factor of expanding restriction, molecular sieve intergrowth simultaneously, the content of molecular sieve can reach more than 98%, thus substantially increases the intensity of catalyzer.Adopt the inventive method, catalyst utilization is high, and activity can up to 91%, good stability, and catalyst regeneration cycle can reach more than 2 years, achieves good technique effect.
Further instruction is given to the present invention below by embodiment.
Embodiment
[embodiment 1]
Take the former powder (SiO of NaY type
2/ Al
2o
3mol ratio is 3.53) the former powder 40g of Y zeolite, sodium aluminate 5.217g, sodium hydroxide 5g, silica 1 6g, deionized water 24g.Be put in ceramic mortar and mix.Extruded moulding.Dry in 110 DEG C of baking ovens and spend the night, roasting 6 hours in 550 DEG C of retort furnaces.Be placed in Autoclaves for synthesis, bottom synthesis reactor, fill deionized water, put shaping catalyzer with stainless (steel) wire on reactor top, ensure that catalyzer does not contact with water.Then 120 DEG C of crystallization 10 hours.Use deionized water wash 2 times after taking out, dry, for subsequent use after roasting.
Subsequently, the catalyzer weight concentration after roasting be 10% ammonium nitrate solution ammonium hand over, to stir 4 hours at 90 DEG C, centrifuging, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 4 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Then stop passing into water vapor, be down to room temperature, then be the aqueous ammonium nitrate solution of 10% with weight concentration, stirring 4 hours at 90 DEG C, with deionized water wash 2 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours, namely obtain finished catalyst.
[embodiment 2 ~ 9]
With [embodiment 1], just shaping ratio is different with Crystallizing treatment condition.Specifically in table 1.
Table 1
[embodiment 10]
Investigate catalyst reaction performance with fixed-bed reactor from bottom to top, reactor is the stainless steel tube of internal diameter 28 millimeters, length 800 millimeters.Loaded catalyst is 3 grams, and is diluted to 10ml with granulated glass sphere.
After the catalyst loading of [embodiment 1 ~ 9] is entered reactor, under nitrogen protection catalyzer is activated, at 400 DEG C, activate 1 hour.Then be cooled to less than 40 DEG C, stop nitrogen purging, start into transalkylation material, after the value that pressure reaches set, start to be warming up to temperature of reaction.
Reaction conditions is: temperature 170 DEG C, pressure 3.0MPa, liquid phase air speed 2.5 hours
-1, benzene and diethylbenzene weight ratio 1:1.After system stability, timing is got product liquid and is carried out stratographic analysis.Following data are all the charging stable data of 10 hours, specifically in table 2.
[comparative example 1]
Take the former powder (SiO of NaY type of ordinary method synthesis
2/ Al
2o
3than being 3.53) the former powder 40g of Y zeolite, be that 80:20 is shaping with aluminum oxide according to butt weight ratio, with post-drying, roasting.
By weight concentration be subsequently 10% ammonium nitrate solution in, to stir 4 hours at 90 DEG C, centrifuging, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 4 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Then stop passing into water vapor, be down to room temperature, then be the aqueous ammonium nitrate solution of 10% with weight concentration, stirring 4 hours at 90 DEG C, with deionized water wash 2 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Namely finished catalyst is obtained.Then investigate catalyzer initial activity with [embodiment 10], the results are shown in Table 2.
Table 2
By carrying out XRD spectra analysis to the catalyzer before and after crystallization, can find that the degree of crystallinity of crystallization rear catalyst increases; This shows that the binding agent part between molecular sieve there occurs conversion, and the molecular sieve content of catalyzer is added.As can be seen from Table 2, the catalyzer of identical weight, binder free catalyzer due to the content of molecular sieve high, mass transfer velocity is fast, and catalyzer can bear higher air speed, and the intensity of catalyzer have also been obtained and significantly improves simultaneously.
[comparative example 2]
Take the former powder (SiO of USY type of ordinary method synthesis
2/ Al
2o
3than being 5.53) the former powder 40g of Y zeolite, be that 80:20 is shaping with aluminum oxide according to butt weight ratio, with post-drying, roasting.
By weight concentration be subsequently 10% ammonium nitrate solution in, to stir 4 hours at 90 DEG C, centrifuging, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 4 times.Subsequently in 550 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Then stop passing into water vapor, be down to room temperature, then be the aqueous ammonium nitrate solution of 10% with weight concentration, stirring 4 hours at 90 DEG C, with deionized water wash 2 times.
[embodiment 11]
Investigate catalyst reaction performance with fixed-bed reactor from bottom to top, reactor is the stainless steel tube of internal diameter 28 millimeters, length 800 millimeters.Loaded catalyst is 3 grams, and is diluted to 10ml with granulated glass sphere.
By [embodiment 1 ~ 9], after the catalyst loading of [comparative example 1,2] enters reactor, under nitrogen protection catalyzer is activated, at 400 DEG C, activate 1 hour.Then be cooled to less than 40 DEG C, stop nitrogen purging, start into transalkylation material, after the value that pressure reaches set, start to be warming up to temperature of reaction.
Reaction conditions is: temperature 240 DEG C, pressure 4.0MPa, total liquid phase air speed 7.0 hours
-1, benzene and diethylbenzene weight ratio 1:1.After system stability, timing is got product liquid and is carried out stratographic analysis.Following data are all the charging stable data of 10 hours, specifically in table 3.
Table 3
| Catalyzer | Diethylbenzene transformation efficiency, % | Ethylbenzene selectivity, % | Deactivation rate, %/hour |
| Embodiment 1 | 60.17 | 98.11 | 0.115 |
| Embodiment 2 | 68.35 | 99.15 | 0.196 |
| Embodiment 3 | 67.71 | 99.38 | 0.185 |
| Embodiment 4 | 66.59 | 99.66 | 0.190 |
| Embodiment 5 | 60.57 | 99.13 | 0.195 |
| Embodiment 6 | 65.39 | 99.22 | 0.110 |
| Embodiment 7 | 63.15 | 99.14 | 0.290 |
| Embodiment 8 | 61.17 | 98.62 | 0.390 |
| Embodiment 9 | 41.26 | 95.55 | 0.385 |
| Comparative example 1 | 37.02 | 97.54 | 0.405 |
| Comparative example 2 | 47.02 | 97.68 | 0.425 |
As can be seen from Table 3, because the active component content of binder free catalyzer is high, active better, simultaneously without covering and the parcel of binding agent, the mass transfer ability of catalyzer improves, and product is easier to diffuse out, and be unlikely to accumulation inactivation, so activity stability is better.
Claims (10)
1. a method for liquid phase transfer, with multi-ethyl phenenyl and benzene for reaction raw materials, temperature of reaction 100 ~ 260 DEG C, reaction pressure 2.0 ~ 4.5MPa, liquid phase weight air speed 1 ~ 10 hour
-1, under the condition of benzene/multi-ethyl phenenyl weight ratio 1 ~ 10, reaction raw materials and catalyst exposure generation liquid phase shift reaction generate ethylbenzene; Wherein, described catalyzer is SiO
2/ Al
2o
3mol ratio is the binder free Y zeolite of 3 ~ 20.
2. the method for liquid phase transfer according to claim 1, is characterized in that, in described binder free Y zeolite, the content of molecular sieve is greater than 95 % by weight.
3. the method for liquid phase transfer according to claim 1, is characterized in that described binder free Y zeolite SiO
2/ Al
2o
3mol ratio is 3 ~ 20.
4. the method for liquid phase transfer according to claim 1, is characterized in that described binder free Y zeolite is through steam-treated.
5. the method for liquid phase transfer according to claim 4, it is characterized in that steam-treated temperature is 400 ~ 800 DEG C, the treatment time is 0.5 ~ 24 hour, and the weight space velocity of water vapour is 1 ~ 10 hour
-1.
6. the method for liquid phase transfer according to claim 1, is characterized in that temperature of reaction is 150 ~ 240 DEG C.
7. the method for liquid phase transfer according to claim 1, is characterized in that reaction pressure is 2.5 ~ 4.0MPa.
8. the method for liquid phase transfer according to claim 1, is characterized in that liquid phase weight air speed is 1 ~ 5 hour
-1.
9. the method for liquid phase transfer according to claim 1, is characterized in that benzene/multi-ethyl phenenyl weight ratio is 1 ~ 5.
10. the method for liquid phase according to claim 1 transfer, is characterized in that the many ethylbenzene of raw material is pure ethylene method, rare ethylene process or alcohol legal system is for the many ethylbenzene produced in ethylbenzene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107511168A (en) * | 2016-06-18 | 2017-12-26 | 中国石油化工股份有限公司 | The preparation method of Adhesive-free Molecular Sieve catalyst |
| CN112707410A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | USY type molecular sieve and preparation method and application thereof |
| WO2021210674A1 (en) * | 2020-04-16 | 2021-10-21 | 日揮触媒化成株式会社 | Faujasite type zeolite and method for producing same |
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| EP0733608A1 (en) * | 1995-03-21 | 1996-09-25 | Fina Technology, Inc. | Transalkylation of polyalkylaromatic hydrocarbons |
| CN102371169A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Binder-free molecular sieve catalyst and its preparation method |
| CN102746096A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for liquid phase transalkylation of polyethylbenzene and benzene |
-
2013
- 2013-06-17 CN CN201310236993.8A patent/CN104230633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0733608A1 (en) * | 1995-03-21 | 1996-09-25 | Fina Technology, Inc. | Transalkylation of polyalkylaromatic hydrocarbons |
| CN102371169A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Binder-free molecular sieve catalyst and its preparation method |
| CN102746096A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for liquid phase transalkylation of polyethylbenzene and benzene |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107511168A (en) * | 2016-06-18 | 2017-12-26 | 中国石油化工股份有限公司 | The preparation method of Adhesive-free Molecular Sieve catalyst |
| CN107511168B (en) * | 2016-06-18 | 2021-03-30 | 中国石油化工股份有限公司 | Preparation method of binder-free molecular sieve catalyst |
| CN112707410A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | USY type molecular sieve and preparation method and application thereof |
| CN112707410B (en) * | 2019-10-24 | 2022-08-12 | 中国石油化工股份有限公司 | USY type molecular sieve and preparation method and application thereof |
| WO2021210674A1 (en) * | 2020-04-16 | 2021-10-21 | 日揮触媒化成株式会社 | Faujasite type zeolite and method for producing same |
| JPWO2021210674A1 (en) * | 2020-04-16 | 2021-10-21 | ||
| JP7145343B2 (en) | 2020-04-16 | 2022-09-30 | 日揮触媒化成株式会社 | Faujasite-type zeolite and method for producing the same |
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Application publication date: 20141224 |