CN1087555A - The catalyzer of ethene and the direct synthesizing styrene of benzene - Google Patents
The catalyzer of ethene and the direct synthesizing styrene of benzene Download PDFInfo
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- CN1087555A CN1087555A CN93107737A CN93107737A CN1087555A CN 1087555 A CN1087555 A CN 1087555A CN 93107737 A CN93107737 A CN 93107737A CN 93107737 A CN93107737 A CN 93107737A CN 1087555 A CN1087555 A CN 1087555A
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- CN
- China
- Prior art keywords
- catalyst
- benzene
- reaction
- zeolite
- carrier
- Prior art date
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 60
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010457 zeolite Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 2
- 150000001340 alkali metals Chemical class 0.000 claims abstract 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract 2
- 150000002910 rare earth metals Chemical class 0.000 claims abstract 2
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 10
- 230000029936 alkylation Effects 0.000 abstract description 3
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 238000004939 coking Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- VSJQKKBXZDSXIX-UHFFFAOYSA-N ethylbenzene styrene toluene Chemical compound CC1=CC=CC=C1.CCC1=CC=CC=C1.C=CC1=CC=CC=C1 VSJQKKBXZDSXIX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了乙烯与苯直接合成苯乙烯的催化 剂，它由碱金属，碱土金属及稀土金属，过渡金属等元 素组成的活性组分负载在沸石分子筛载体上而成。 该催化剂同时具有烷基化和脱氢性能，在反应压力 0.1～1MPa，反应温度400～700℃，苯/乙烯比＝ (1.0～15.0)/1.0，空速(gC2H4/gCat·h)＝0.2～ 2.0h-1的反应条件下，可高活性(C2H4转化率可高达 100％)、高选择性(苯乙烯的选择性可高达65.2％) 地将乙烯与苯一步合成苯乙烯，既缩短了工艺流程， 又可减少投资，降低能耗。The invention discloses a catalyst for directly synthesizing styrene from ethylene and benzene. The catalyst is composed of alkali metals, alkaline earth metals, rare earth metals, transition metals and other elements loaded on a zeolite molecular sieve carrier. The catalyst has both alkylation and dehydrogenation properties. The reaction pressure is 0.1-1MPa, the reaction temperature is 400-700°C, the benzene/ethylene ratio = (1.0-15.0)/1.0, and the space velocity (gC 2 H 4 /gCat·h )=0.2 ～ 2.0h -1 under the reaction conditions, it can synthesize ethylene and benzene in one step with high activity (the conversion rate of C2H4 can be as high as 100%) and high selectivity (the selectivity of styrene can be as high as 65.2%) Styrene not only shortens the process flow, but also reduces investment and energy consumption.
Description
The present invention relates to a kind of ethene and benzene one-step synthesis vinylbenzene catalyst for reaction.
Vinylbenzene is to produce plastics and elastomeric important source material, and producing cinnamic method at present both at home and abroad all is to adopt two step method, at first generates ethylbenzene by benzene and ethylene alkylation, generates vinylbenzene by ethylbenzene dehydrogenation again, promptly
The △ G of " single stage method "
0
(3)=16.02KJ/mol is than the △ G of dehydrogenation reaction
0
(2)Much smaller, K
P3=1.56 * 10
-3K than dehydrogenation reaction
P2Much bigger, be easy to break through the equilibrated restriction, so " single stage method " reaction is more much easier than dehydrogenation reaction.By benzene and ethene " single stage method " directly the key of the reaction of synthesizing styrene be the research of catalyzer." single stage method " catalyst for reaction should have alkylating, and dehydrogenation functionality is arranged again.
The object of the invention provides a kind of ethene and direct synthesizing styrene catalyst for reaction of benzene " single stage method " of being used for, for a new route of synthesis is opened up in cinnamic production.
Catalyzer of the present invention is to load on the carrier with active constituent to form.Its carrier is a zeolite molecular sieve, and active phase composite is AaBbOx, and wherein A is a basic metal, alkaline-earth metal and thulium (as Li, K, Rb, Cs, Mg, La, elements such as Ce) one or more in, B are transition metal and III A, IV A, V A, and VI A family element (as V, Cr, Mo, W, Mn, Fe, Co, Ni, Pt and Bo, Sn, Pb, P, elements such as Bi) one or more in, the content of carrier is 10～90%wt usually, each element a, the relative content of b (based on carrier) is respectively a=0.1～10, b=0.1～20, the content commonly used of carrier is 40～80%wt, a, the best relative content (based on carrier) of b is respectively a=0.2～0.5, b=0.4～10.
Preparation of catalysts method of the present invention is as follows: (1) zeolite molecular sieve is used NH earlier under 50～100 ℃
4Cl is exchanged into NH
4The type zeolite is used the NH of 5%～10%wt usually
4Cl is exchanged into NH by liquid-solid ratio 2/1～10/1
4The type zeolite got H type zeolite in 3～5 hours then 110 ℃ of oven dry down, and 400～550 ℃ of following roastings; (2) with pickling process with active constituent loading on H type zeolite, after the drying again under 400～700 ℃, 3～18 hours zeolite catalysts that get product of roasting in the air atmosphere.
Catalyzer of the present invention is used for ethene and the cinnamic reaction of benzene one-step synthesis, at reaction pressure 0.1～1.0MPa, and 400 ℃～700 ℃ of temperature of reaction, benzene/ethene=(1.0～15.0)/1.0, air speed (gC
2/ H
4/ gCat.h)=0.2～2.0 h
-1Reaction conditions under, C
2H
4Transformation efficiency can be up to 100%, cinnamic selectivity can be up to 65.2%.
Catalyzer of the present invention has alkylation and dehydrogenation functionality simultaneously, is used for ethene and benzene synthesizing styrene, can directly synthesize in " step ", thereby opened up a new way for vinylbenzene is synthetic, not only but shortened process reduces investment cost, but also can cut down the consumption of energy.
Further specify the present invention by the following examples.
Example 1, this routine carrier HZSM-5 zeolite molecular sieve, the activity of such catalysts component contains Mg, La, P, Fe element.Earlier the NaZSM-5 zeolite molecular sieve is used 10%wt NH down at 95 ℃
4Cl gets NH 3 times by liquid-solid ratio 5/1 exchange
4ZSM-5,110 ℃ of oven dry down, 550 ℃ of following roastings obtained the HZSM-5 zeolite in 5 hours, with (the NH of capacity then
4) H
2PO
4The aqueous solution place beaker with the P(of load 10%wt based on HZSM-5), in addition with the OMg(NO of capacity
3)
26H
2The O aqueous solution also place beaker with the Mg(of load 5%wt based on HZSM-5), the La(NO of capacity
3) O
3XH
2O(La
2O
3Content is 40%) aqueous solution also is added in the beaker, with the La(of load 0.5%wt based on HZSM-5), again with (NH
4)
3Fe(C
2O
4)
33H
2The O aqueous solution also is added in the beaker with load α-Fe
2O
3, 10%wt(is based on HZSM-5), adding the volume that water makes steeping fluid volume and carrier simultaneously is 1: 1.The good back of dipping 110 ℃ dry down, 650 ℃ of following roastings 12 hours, catalyzer gets product.Contain 4.8%wt Mg in the catalyzer, 0.48%wt La, 9.5%wt P, 9.6%wt α-Fe
2O
3(based on carrier HZSM-5).
Example 2, this routine carrier HZSM-5 zeolite molecular sieve, the activity of such catalysts component contains Mg, La, P, Fe, Pt, Sn element.Its preparation process is with example 1, and steeping fluid is except using (NH
4) H
2PO
4, Mg(NO
3)
26H
2O, La(NO
3)
2XH
2O, (NH
4)
3Fe(C
2O
4)
33H
2Outside the O, the Platinic chloride that also adds capacity with the Pt(of load 0.4%wt based on HZSM-5), also add an amount of SnCl simultaneously
45H
2O is with the Sn of load 0.5%wt, and adding water at last, to make the volume of steeping fluid and the volume ratio of carrier be 1: 1, after dipping is good, 110 ℃ dry down, and 650 ℃ of following roastings 12 hours, catalyzer got product.Contain 4.8%wt Mg in the catalyzer, 0.46%wt La, 9.6%wt P, 9.8%wt α-Fe
2O
3, 0.38%wt Pt, 0.49%wt Sn(is based on carrier HZSM-5).
Example 3, ethene and the cinnamic reaction of benzene one-step synthesis, catalyst system therefor is example 1 catalyzer.Catalyzer activates 2 hours under 550 ℃ earlier in air atmosphere, be 500～600 ℃ in temperature of reaction, and reaction pressure is normal pressure (0.1MPa), and benzene/ethylene ratio is 10/1, air speed (gC
2H
4Under/gCat.h)=1.0 reaction conditions, C
2H
4Transformation efficiency be 100%, toluene, ethylbenzene, cinnamic selectivity are respectively 7.7%, 61.8%, 30.5%.
Example 4, ethene and the cinnamic reaction of benzene one-step synthesis, catalyst system therefor is example 2 catalyzer.Catalyzer activates 2 hours under 550 ℃ earlier in air atmosphere, be 500～600 ℃ in temperature of reaction, and reaction pressure is normal pressure (0.1MPa), and benzene/ethylene ratio is 10/1, air speed (gC
2H
4Under/gCat.h)=1.0 reaction conditions, C
2H
4Transformation efficiency be 100%, toluene, ethylbenzene, cinnamic selectivity are respectively 6.3%, 28.5% and 65.2%.
The table I is the performance of each preformed catalyst.
The table I
| Catalyzer composition/carrier | C 2H 4Transformation efficiency | Selectivity | ||
| Toluene | Ethylbenzene | Vinylbenzene | ||
| 0.50%La,9.6%Fe 2O 3/HZSM-5 | 85.3% | 3.4% | 77.8% | 18.8% |
| 0.64%La,0.32%Cs, 9.6%Fe 2O 3/HY | 62.8% | 9.2% | 64.4% | 26.4% |
| 4.8%Mg,0.48La,9.5%P, 9.6%Fe 2O 3/HZSM-5 | 100% | 7.7% | 61.8% | 30.5% |
| 4.8%Mg,0.46%La,9.6%P, 9.8%Fe 2O 3,0.38%Pt, 0.4%Sn/HZSM-5 | 100% | 6.3% | 28.5% | 65.2% |
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93107737A CN1087555A (en) | 1993-06-30 | 1993-06-30 | The catalyzer of ethene and the direct synthesizing styrene of benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93107737A CN1087555A (en) | 1993-06-30 | 1993-06-30 | The catalyzer of ethene and the direct synthesizing styrene of benzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1087555A true CN1087555A (en) | 1994-06-08 |
Family
ID=4986816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93107737A Pending CN1087555A (en) | 1993-06-30 | 1993-06-30 | The catalyzer of ethene and the direct synthesizing styrene of benzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1087555A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323753C (en) * | 2005-03-01 | 2007-07-04 | 华东理工大学 | Catalyst used for preparing phenylethylene and its application |
| CN100402142C (en) * | 2006-03-29 | 2008-07-16 | 上海华谊丙烯酸有限公司 | Catalyst for synthesizing allyl alcohol by reduction of acrolein and preparation method thereof |
| CN100453175C (en) * | 2004-09-30 | 2009-01-21 | 友联有机合成化学有限公司 | Catalyst and its preparation method and use of the said catalyst in 5h-dibenzanthracene-(b,f)-aza |
| CN101306367B (en) * | 2007-05-18 | 2010-05-19 | 中国石油化工股份有限公司 | Sulfurated hydrogen gas containing catalytic incineration catalyst and preparation method thereof |
| CN112495428A (en) * | 2020-12-30 | 2021-03-16 | 北京交通大学 | Catalyst for catalyzing n-hexane aromatization reaction through rail regulation and control, preparation method and application |
-
1993
- 1993-06-30 CN CN93107737A patent/CN1087555A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453175C (en) * | 2004-09-30 | 2009-01-21 | 友联有机合成化学有限公司 | Catalyst and its preparation method and use of the said catalyst in 5h-dibenzanthracene-(b,f)-aza |
| CN1323753C (en) * | 2005-03-01 | 2007-07-04 | 华东理工大学 | Catalyst used for preparing phenylethylene and its application |
| CN100402142C (en) * | 2006-03-29 | 2008-07-16 | 上海华谊丙烯酸有限公司 | Catalyst for synthesizing allyl alcohol by reduction of acrolein and preparation method thereof |
| CN101306367B (en) * | 2007-05-18 | 2010-05-19 | 中国石油化工股份有限公司 | Sulfurated hydrogen gas containing catalytic incineration catalyst and preparation method thereof |
| CN112495428A (en) * | 2020-12-30 | 2021-03-16 | 北京交通大学 | Catalyst for catalyzing n-hexane aromatization reaction through rail regulation and control, preparation method and application |
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Applicant after: Zhejiang University Applicant after: China Petrochemical Corporation Applicant before: Zhejiang University |
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