CN106881146A - It is a kind of for dry gas and the preparation method of the molecular sieve catalysts of benzene alkylation reaction F ZSM 11 - Google Patents
It is a kind of for dry gas and the preparation method of the molecular sieve catalysts of benzene alkylation reaction F ZSM 11 Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
The invention provides a kind of for dry gas and the preparation method of the molecular sieve catalysts of benzene alkylation reaction F ZSM 11, comprise the following steps that：It is in synthesis reactor that ammonium fluoride, water, silicon source, silicon source, NaOH, TBABr (TBAB) and CTAB (cetyl ammonium bromide) is well mixed, mol ratio is obtained for 12Na2O:(0.05~0.30) F:(1~1.8) Al2O3:(80~120) SiO2:2TBABr:(0.25~10) CTAB:3600H2The aggregate sample of O, in 150~180 DEG C of crystallization temperature, revolution is to synthesize 12~24h under the conditions of 60~100rpm, then room temperature, washing to drying and roasting after neutrality, then with the ammonium nitrate solution of 0.5~1.0mol/L in 70~90 DEG C of exchanges are dropped to, dry roasting, is made H type molecular sieve catalysts.Synthesize the molecular sieve catalysts of F ZSM 11 under TBABr of the invention and CTAB collective effects, compared with the conventional molecular sieve catalysts of F ZSM 11 for only being synthesized with TBABr, conversion of ethylene is higher in dry gas, and xylene content is greatly lowered in product.
Description
Technical field
The invention belongs to petrochemical industry, and in particular to one kind is used for dry gas and benzene alkylation reaction F-ZSM-11 molecules
The preparation method of sieve catalyst..
Background technology
Catalytic cracked dry gas are the tail gas of refinery's by-product, wherein containing ethene 12-25% (volume fraction).At present, China
Catalytic cracking unit scale occupies second place of the world, the ethene considerable amount in dry gas.Generally burnt dry gas as fuel gas
Fall, both cause atmosphere pollution, waste the ethene resource of preciousness；Ethylbenzene manufactured from ethylene is that simple and effective dry gas is straight in dry gas
Connect and utilize technology, it is commonplace in the application of China.
From the '30s end since developed it is various with ethene and benzene as the process of raw material ethylbenzene.In the seventies
Phase, Mobil companies of the U.S. reported in USP3751506 using HZSM-5 molecular sieve catalysts for vapor phase method carry out benzene with
Pure ethylene alkylated reaction.USP4,107,224 discloses a kind of ethene in the presence of HZSM-5 zeolite catalysts to dilute
Take the process of ethylbenzene for raw material gas phase legal system, dilute ethene is also retrieved from the tail gas of the catalytic cracking unit of refinery, but with
The tail gas need to remove H before making raw material2S、CO2、H2O and C2Residue above.
US3962364 discloses the catalyst that a kind of P elements are modified to ZSM-5 zeolite, by modified, catalysis
Agent has obtained certain raising to the stability of the selectivity and catalyst of benzene and ethylene reaction.The conversion ratio of ethene is reachable
98%, the selectivity that ethylizes is up to 98.99%.Steam treatment is disclosed in US4016218 to improve catalyst second when reacting
The selectivity of base.
CN00111720.3 discloses a kind of method for improving benzene and ethene vapor-phase alkylation ZSM-5 catalyst stabilities,
After carrying out steam treatment to ZSM-5 molecular sieve catalyst, then organic acid treatment is used, preferably overcome conversion of ethylene
The shortcoming of not high enough and catalyst activity stability difference, preferably can be used in industrial production.
One kind is disclosed in CN99112833.8 and USP 6093866 to be urged in rare earth-HZSM-5/ZSM-11 cocrystallization zeolites
The method that dilute ethene and/or propylene produce ethylbenzene and/or propyl benzene with benzene reaction in the presence of agent.It is dry with the catalysis from refinery
Gas, is not required to refine in advance, and catalysis drying gas carry out vapour phase hydrocarbonylation, the diethyl of by-product with benzene in multistage, cold shock alkylation reaction device
Benzene carries out liquid phase reverse alkylation in a fixed bed reactors.
Micro- mesoporous composite molecular sieve has micropore and mesoporous dual model pore size distribution, combine the duct advantage of mesoporous material with
The highly acid and high hydrothermal stability of micro porous molecular sieve, can make two kinds of material advantage complementations, synergy.Microporous mesoporous compound point
The gradient distribution of sub- mesh size is reasonably combined with acidity, will produce beneficial cooperative effect, there is wide in terms of absorption and catalysis
Wealthy application prospect.Alkali process are the effective ways for manufacturing microporous mesoporous composite molecular screen.Li Yu rather wait [Y.Li, S.Liu,
S.Xie, L.Xu, Appl.Catal.A 360 (2009) 8~16] report it is microporous mesoporous multiple through the Zn/ZSM-5 of alkali treatment modifying
Close molecular sieve catalyst and superior reaction stability is shown during 1- hexene aromatizations.Sadowska etc.
[K.Sadowska,A.Wach,Z.Olejniczak,P.J.Datka,Microporous and
Mesoporous Materials 167 (2013) 82~88.] research find with soda ash treatment compared with, the addition of surfactant
The mesoporous of more narrowly distributings can be produced.Yoo etc. [W.C.Yoo, X.Zhang, M.Tsapatsis, A.Stein,
Micropor.Mesopor.Mater.149 (2012) 147~157] find compared with common alkali process, at surfactant alkali
The ZSM-5 molecular sieve that reason is obtained has crystallinity and more excellent pore structure property higher.Schmidt etc. [F.Schmidt,
M.R.Lohe,B.Büchner,F.Giordanino,F.Bonino,S.Kaskel,Micropor.Mesopor.Mater.165
(2013) 148~157] ZSM-5 molecular sieve shows more in methyl alcohol converts hydrocarbon reaction processed after finding surfactant alkali process
Strong stability.[K.Sadowska, K.G the ó ra-Marek, J.Datka, Vibrational such as Sadowska
Spectroscopy 63 (2012) 418~425.] report compared with soda ash solution, surfactant and aqueous slkali common point
Due to mesoporous effective generation after reason ZSM-5 molecular sieve, hence it is evident that improve sour position accessibility.
Although ZSM-5 and ZSM-11 are ZSM Series Molecules sieve, but the former belongs to MFI topological structures (by the straight line for intersecting
Type hole road and sinusoidal duct composition), the latter is MEL topological structures (cross one another straight hole road), and skeleton structure is poor in the presence of some
It is different, it is mainly reflected on the crosspoint in duct.Tinkling of pieces of jade etc. [L.Zhang, H.Liu, X.Li, S.Xie, Y.Wang, W.Xin,
S.Liu, L.Xu, Fuel Process.Technol.91 (2010) 449~455] find and with similar acid and particle size
ZSM-5 molecular sieve compare, ZSM-11 shows aromatics yield higher in 1- hexene aromatization reactions.
In dry gas and benzene vapor-phase alkylation product in addition to ethylbenzene, diethylbenzene and triethylbenzene (TEB), also dimethylbenzene, toluene and three
Toluene etc., wherein dimethylbenzene and ethylbenzene are particularly difficult to separate, and how to reduce xylene content in product, improve ethylbenzene product matter
Amount, is always the direction of the subject study, using the acid and mesoporous diffusion of micropore, i.e., using micro- mesoporous composite molecular
Sieve carries out dry gas and benzene vapor-phase alkylation is likely to decrease xylene content in product.In this context, we TBABr with
Synthesize the micro- mesoporous composite molecular sieves of F-ZSM-11 under CTAB collective effects and be used for dry gas and benzene alkylation reaction.
The content of the invention
It is an object of the invention to provide a kind of for dry gas and benzene alkylation reaction F-ZSM-11 molecular sieve catalysts
Preparation method, compared with the conventional F-ZSM-11 molecular sieve catalysts for only being synthesized with TBABr, by TBABr of the present invention
Conversion of ethylene is higher in dry gas with synthesizing under CTAB collective effects on F-ZSM-11 molecular sieve catalysts, and dimethylbenzene contains in product
Amount is greatly lowered.
The invention provides a kind of for dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts,
Comprise the following steps that：Ammonium fluoride, water, silicon source, silicon source, NaOH, TBABr and CTAB are well mixed in synthesis reactor, are rubbed
You are than being 12Na2O:(0.05~0.30) F:(1~1.8) Al2O3:(80~120) SiO2:2TBABr:(0.25~10) CTAB:
3600H2The aggregate sample of O, in 150~180 DEG C of crystallization temperature, revolution is to synthesize 12~24h under the conditions of 60~100rpm, is then dropped
To room temperature, washing to drying and roasting after neutrality is then exchanged with the ammonium nitrate solution of 0.5~1.0mol/L in 70~90 DEG C, dry
Roasting, is made H- type molecular sieve catalysts after dry.
It is described provided by the present invention for dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts
Silicon source be in aluminum sulfate and aluminum oxide one or two.
It is described provided by the present invention for dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts
Silicon source is one or more in silica gel, White Carbon black and Ludox.
It is described provided by the present invention for dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts
CTAB/TBABr mol ratios are 0.25~4：1.
Provided by the present invention for dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts, crystallization
160~170 DEG C of temperature, revolution is 70~80rpm, 14~18h of crystallization time.
Dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts that the present invention is provided, drying temperature
It it is 90~130 DEG C, drying time is 2~12h, sintering temperature is 450~600 DEG C, and roasting time is 2~8 hours.
The present invention prepares the Na in F-ZSM-11 molecular sieve catalysts2O content is less than or equal to 0.05wt%.
The present invention is simple to operation, and a step can synthesize, in addition the high income of molecular sieve catalyst.
The benzene feedstock that the present invention is used is the mixture of industrial purified petroleum benzin, or benzene and ethene and benzene-alkylation product.It is former
Material gas is the dry gas (being referred to as dry gas) of catalytic cracking or catalytic pyrolysis, and benzene is not required to dehydration, and typically aqueous is 100-1000ppm,
Catalysis drying gas are not required to purification, such as not desulfurization, be not dehydrated, not deoxidation, not de- COx etc., catalysis drying gas 10-60%v containing ethene contains
H2S 100-5000ppm, 1.0-5.0%v containing COx, oxygen-containing 0.1-1.5%v, aqueous is 1000-4000ppm.
The present invention will synthesize F-ZSM-11 molecular sieve catalysts under TBABr and CTAB collective effects be used for dry gas and benzene alkyl
Change reaction, compared with the conventional F-ZSM-11 molecular sieve catalysts for only being synthesized with TBABr, conversion of ethylene can be obtained further
Improve, xylene content significantly declines in product.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Comparative example 1
By 2.24g Al in stainless steel synthesis reactor2(SO4)3·18H2O (99.0wt%, as follows) is dissolved in 20ml water,
By 39.07g Ludox (25.59wt%SiO under conditions of stirring2, 0.31wt%Na2O, 0.10wt%Al2O3,
73.99wt%H2It is O, as follows), 1.72gNaOH (96.0wt%, as follows), 1.20gTBABr (99.0wt%, it is as follows according to
Secondary addition is well mixed, and by metering than remaining water is added, obtains mol ratio for 12Na2O:1.8Al2O3:90SiO2:
2TBABr:3600H2The aggregate sample of O, then by the aggregate sample in 160 DEG C of crystallization temperature, revolution is to synthesize under the conditions of 70rpm
16h, then drops to room temperature, is dried after washing to neutrality, 550 DEG C of roasting 6h, then with the ammonium nitrate solution of 0.8mol/L in 85
DEG C three times (1 hour/time) is exchanged, wash three times (1 hour/time), 110 DEG C dry 10h, be calcined at 510 DEG C after 4h to be obtained and urge
Agent Cat-A, detects, the Na in the catalyst through XRF2O is less than 0.05wt%.
Comparative example 2
By 2.24g Al in stainless steel synthesis reactor2(SO4)3·18H2O (99.0wt%, as follows) is dissolved in 20ml water,
By 39.07g Ludox (25.59wt%SiO under conditions of stirring2, 0.31wt%Na2O, 0.10wt%Al2O3,
73.99wt%H2O, as follows), 1.72gNaOH (96.0wt%, as follows), 1.20gTBABr (99.0wt%, as follows),
0.014g NH4F sequentially add it is well mixed, by metering than by remaining water add, obtain mol ratio be 12Na2O:0.2F:
1.8Al2O3:90SiO2:2TBABr:3600H2The aggregate sample of O, then by the aggregate sample in 160 DEG C of crystallization temperature, revolution is
Synthesize 16h under the conditions of 70rpm, then drop to room temperature, dried after washing to neutrality, 550 DEG C of roasting 6h, then with 0.8mol/L's
Ammonium nitrate solution exchanges three times (1 hour/time) in 85 DEG C, washes three times (1 hour/time), and 110 DEG C dry 10h, at 510 DEG C
Catalyst Cat-B is obtained after roasting 4h, is detected through XRF, the Na in the catalyst2O is less than 0.05wt%.
Embodiment 1
By 2.24g Al in stainless steel synthesis reactor2(SO4)3·18H2O is dissolved in 20ml water, will under conditions of stirring
39.07g Ludox, 1.72g NaOH, 1.20gTBABr, 3.40g CTAB (99.0wt%, as follows), 0.014g NH4F according to
Secondary addition is well mixed, and by metering than remaining water is added, obtains mol ratio for 12Na2O:0.2F:1.8Al2O3:90SiO2:
2TBABr:5CTAB:3600H2The aggregate sample of O, then by the aggregate sample in 160 DEG C of crystallization temperature, under the conditions of revolution is 70rpm
Synthesis 16h, then drops to room temperature, is dried after washing to neutrality, 550 DEG C of roasting 6h, then with the ammonium nitrate solution of 0.8mol/L
Three times (1 hour/time) is exchanged in 85 DEG C, three times (1 hour/time) is washed, 110 DEG C dry 10h, made after being calcined 4h at 510 DEG C
Catalyst Cat-C is obtained, is detected through XRF, the Na in the catalyst2O is less than 0.05wt%.
Embodiment 2
By 1.88g Al in stainless steel synthesis reactor2(SO4)3·18H2O and 0.05g aluminum oxide is dissolved in 20ml water, is being stirred
By 23.45g Ludox under conditions of mixing, 4.37g silica gel (91.5wt%), 1.75gNaOH, 1.20gTBABr, 1.70g CTAB,
0.007g NH4F sequentially add it is well mixed, by metering than by remaining water add, obtain mol ratio be 12Na2O:0.1F:
1.8Al2O3:90SiO2:2TBABr:0.25CTAB:3600H2The aggregate sample of O, then by the aggregate sample in 150 DEG C of crystallization temperature,
Then revolution drops to room temperature to synthesize 24h under the conditions of 100rpm, is dried after washing to neutrality, 450 DEG C of roasting 8h, then use
The ammonium nitrate solution of 0.5mol/L exchanges three times (1 hour/time) in 90 DEG C, washes three times (1 hour/time), and 130 DEG C dry 5h,
Catalyst Cat-D is obtained after being calcined 2h at 580 DEG C, is detected through XRF, the Na in the catalyst2O is less than 0.05wt%.
Embodiment 3
By 1.17g Al in stainless steel synthesis reactor2(SO4)3·18H2O and 0.03g aluminum oxide is dissolved in 20ml water, is being stirred
By 23.45g Ludox under conditions of mixing, 4.71g white carbons (85.0wt%, as follows), 1.99g NaOH, 1.35gTBABr,
7.66g CTAB,0.024g NH4F sequentially add it is well mixed, by metering than by remaining water addition, obtaining mol ratio is
12Na2O:0.3F:1.0Al2O3:80SiO2:2TBABr:10CTAB:3600H2The aggregate sample of O, then by the aggregate sample in crystallization
Then 180 DEG C of temperature, revolution drops to room temperature to synthesize 12h under the conditions of 80rpm, is dried after washing to neutrality, 550 DEG C of roasting 8h,
Three times (1 hour/time) then is exchanged in 85 DEG C with the ammonium nitrate solution of 0.9mol/L, three times (1 hour/time) is washed, 95 DEG C are done
Dry 11h, catalyst Cat-E is obtained after being calcined 6h at 550 DEG C, is detected through XRF, the Na in the catalyst2O is less than
0.05wt%.
Embodiment 4
By 1.17g Al in stainless steel synthesis reactor2(SO4)3·18H2O and 0.03g aluminum oxide is dissolved in 20ml water, is being stirred
By 23.45g Ludox under conditions of mixing, 4.71g white carbons, 1.31g NaOH, 0.90gTBABr, 2.55g CTAB, 0.004g
NH4F sequentially add it is well mixed, by metering than by remaining water add, obtain mol ratio be 12Na2O:0.07F:1.5Al2O3:
120SiO2:2TBABr:5CTAB:3600H2The aggregate sample of O, then by the aggregate sample in 180 DEG C of crystallization temperature, revolution is 60rpm
Under the conditions of synthesize 18h, then drop to room temperature, dried after washing to neutrality, 550 DEG C of roasting 6h, then with the nitric acid of 0.7mol/L
Ammonium salt solution exchanges three times (1 hour/time) in 75 DEG C, washes three times (1 hour/time), and 90 DEG C dry 12h, and 5h is calcined at 570 DEG C
Catalyst Cat-F is obtained afterwards, is detected through XRF, the Na in the catalyst2O is less than 0.05wt%.
Embodiment 5
By 2.24g Al in stainless steel synthesis reactor2(SO4)3·18H2O is dissolved in 20ml water, will under conditions of stirring
39.07g Ludox, 1.72g NaOH, 1.20gTBABr, 1.70g CTAB, 0.011g NH4F sequentially adds well mixed, presses
Metering obtains mol ratio for 12Na than remaining water is added2O:0.16F:1.8Al2O3:90SiO2:2TBABr:2.5CTAB:
3600H2The aggregate sample of O, then by the aggregate sample in 170 DEG C of crystallization temperature, revolution is to synthesize 20h under the conditions of 90rpm, is then dropped
To room temperature, dried after washing to neutrality, 550 DEG C of roasting 6h are then exchanged three times with the ammonium nitrate solution of 0.7mol/L in 85 DEG C
(1 hour/time), washes three times (1 hour/time), and 120 DEG C dry 8h, and catalyst Cat-G, warp are obtained after being calcined 4h at 550 DEG C
XRF detections, the Na in the catalyst2O is less than 0.05wt%.
Comparative example 1~2 and the reaction evaluating of embodiment 1~5
The catalyst of comparative example 1~2 and the gained of embodiment 1~5 is respectively placed in the fixation that internal diameter continuously flows for 24mm
Catalyst performance evaluation is carried out in bed reactor, the loadings of catalyst are 5g, in N2500 DEG C of activation 1h are warmed up under atmosphere,
Then in N2Atmosphere drops to reaction temperature, and raw material is dry gas and benzene.Reacted product carries out gas-liquid point through cooler cooling
From.Gas and product liquid are constituted with Agilent 7890A chromatographic system analysis, and product liquid uses PONA capillary columns,
Hydrogen flame detector.
The composition of unstripped gas is as shown in table 1.The composition (wt%) of benzene feedstock used：Benzene：99.900；Toluene：0.080；
H2O：0.015；Other：0.005.Alkylation reaction condition and the results are shown in Table 2.As can be seen from the table in the condition and range investigated
Interior, TBABr exists with the conversion ratio of synthesis F-ZSM-11 molecular sieve catalysts Cat-C~upper ethene of Cat-G under CTAB collective effects
More than 99%, ethylene synthesis ethylbenzene selectivity>78%, ethylation products selectivity>96%, the xylene content in ethylbenzene product
<900ppm, and the ZSM-11 molecular sieve catalysts (Cat-A) of only TBABr synthesis and the F-ZSM-11 molecular sieves of only TBABr synthesis
Analog value is respectively 96.45%, 72.94%, 95.83%, 1887ppm and 97.28%, 75.45% on catalyst (Cat-B),
96.15% and 1519ppm.
The composition (v%) of the unstripped gas of table 1
| 9.03 | 14.51 | 1.35 | 35.86 | 23.49 | 12.23 | 0.61 | 1.20 | 0.53 | 0.64 | 3800 | 1800 |
The catalytic reaction evaluation result of the various catalyst of table 2
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (8)
1. a kind of for dry gas and the preparation method of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts, it is characterised in that：
Ammonium fluoride, water, silicon source, silicon source, NaOH, TBABr and CTAB are well mixed in synthesis reactor, obtain mol ratio Na2O：F:Al2O3:
SiO2：TBABr：CTAB：H2O is 12:0.05~0.30:1~1.8：80~120:2:0.25~10:3600 aggregate sample, in crystalline substance
Change 150~180 DEG C of temperature, revolution is 12~24h of synthesis under the conditions of 60~100rpm, room temperature is then dropped to, after washing to neutrality
Drying and roasting, then with the ammonium nitrate solution of 0.5~1.0mol/L in 70~90 DEG C of exchanges, dry roasting is made H- types point
Sub- sieve catalyst.
2. according to a kind of for dry gas and the preparation side of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts described in claim 1
Method, it is characterised in that：Silicon source be in aluminum sulfate and aluminum oxide one or two.
3. according to a kind of for dry gas and the preparation side of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts described in claim 1
Method, it is characterised in that:Silicon source is one or more in silica gel, White Carbon black and Ludox.
4. according to a kind of for dry gas and the preparation side of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts described in claim 1
Method, it is characterised in that：CTAB/TBABr mol ratios are 0.25~4：1.
5. according to a kind of for dry gas and the preparation side of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts described in claim 1
Method, it is characterised in that preferably 160~170 DEG C of crystallization temperature, revolution is preferably 70~80rpm, crystallization time preferably 14~18h.
6. according to a kind of for dry gas and the preparation side of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts described in claim 1
Method, it is characterised in that：Drying temperature is 90~130 DEG C, and drying time is 2~12h.
7. according to a kind of for dry gas and the preparation side of benzene alkylation reaction F-ZSM-11 molecular sieve catalysts described in claim 1
Method, it is characterised in that：Sintering temperature is 450~600 DEG C, and roasting time is 2~8h.
8., according to a kind of application for dry gas and benzene alkylation reaction F-ZSM-11 molecular sieve catalysts of claim 1, it is special
Levy and be：The dry gas 10-60%v containing ethene, H2S 100-5000ppm, COx 1.0-5.0%v, oxygen 0.1-1.5%v, water
It is 1000-4000ppm.
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| CN114057538A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by gas-phase alkylation of ethylene-containing gas and benzene |
| CN114057531A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Synthetic method of ethylbenzene |
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| CN114057538B (en) * | 2020-07-31 | 2023-11-10 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene |
| CN114057531B (en) * | 2020-07-31 | 2024-07-09 | 中国石油化工股份有限公司 | Ethylbenzene synthesis method |
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| CN106881146B (en) | 2019-04-30 |
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