CN101422735B - Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof - Google Patents
Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof Download PDFInfo
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- CN101422735B CN101422735B CN2007101766817A CN200710176681A CN101422735B CN 101422735 B CN101422735 B CN 101422735B CN 2007101766817 A CN2007101766817 A CN 2007101766817A CN 200710176681 A CN200710176681 A CN 200710176681A CN 101422735 B CN101422735 B CN 101422735B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 35
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 239000011135 tin Substances 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000464 lead oxide Inorganic materials 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000001404 mediated effect Effects 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 229960004643 cupric oxide Drugs 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 229940072033 potash Drugs 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DIGZKZLYDYJFHH-UHFFFAOYSA-N [K].[Mo].[Ce].[Fe] Chemical group [K].[Mo].[Ce].[Fe] DIGZKZLYDYJFHH-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- OPEIWUZXPYAAGA-UHFFFAOYSA-N [Ca].[K].[Mo].[Ce].[Fe] Chemical compound [Ca].[K].[Mo].[Ce].[Fe] OPEIWUZXPYAAGA-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229960001759 cerium oxalate Drugs 0.000 description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- -1 methyl isopropyl Chemical group 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- LZWYXMHTTRFGTG-UHFFFAOYSA-N [Ca].[Ca].[Mo].[Ce].[K].[Fe] Chemical compound [Ca].[Ca].[Mo].[Ce].[K].[Fe] LZWYXMHTTRFGTG-UHFFFAOYSA-N 0.000 description 1
- QXQZBDRCFKSYAA-UHFFFAOYSA-N [Cr].[K].[Fe] Chemical compound [Cr].[K].[Fe] QXQZBDRCFKSYAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
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- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing styrene by high-efficiency ethylbenzene dehydrogenation and a preparation method thereof, the catalyst is prepared by adding a Cu-Zn-Pb oxide combination into a catalyst taking Fe-K-Ce-Mo-Mg (or Ca or Mg-Ca) as a main system, then preparing at least one oxide of titanium, zirconium and hafnium and at least one oxide of manganese, tin, cobalt and lanthanum, mixing, molding and activating by a dry method, and the catalyst is prepared at the temperature of 620 ℃ and the liquid space velocity of 1.0h-1Under the condition that the weight ratio of water to oil is 2.0, the conversion rate can reach more than 80.20%, the selectivity can reach more than 95.30%, the catalyst has the characteristics of high selectivity, high stability and the like while the activity of the catalyst is maintained, and the problems in the current industrial application are well solved.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of efficient ethyl benzene dehydrogenation preparation of styrene, this catalyst also can be used for cumene, p-Methylisopropylbenzene dehydrogenation system isopropenylbenzene and to the methyl isopropyl alkenyl benzene.
Background technology
The most devices of the styrene in the whole world all adopt the catalytic dehydrogenation method to produce at present, in several generations, gone through in the development of dehydrogenation, developed into general Fe-series catalyst at present by former zinc system catalyst, the Fe-series catalyst that contains chromium is eliminated owing to chromium easily pollutes environment, the substitute is iron-potassium-cerium-molybdenum series.Ethyl benzene dehydrogenation preparation of styrene belongs to heat absorption, increases molecular reaction, commercial plant generally adopts high-temperature heat insulation negative reaction device, in 580～640 ℃ temperature range, activity of such catalysts increases substantially with the rising of temperature, be subjected to the influence of energy consumption and material, the temperature of reactor generally is controlled at 620～640 ℃, but high temperature is accompanied by the generation of more side reaction, make ethylbenzene conversion generate cinnamic selectivity and reduce greatly, also generally maintain about 15～20 months the service life of catalyst.For this reason, when improving catalyst activity, improve developing direction and the research focus that selection of catalysts, stability and life-span become this catalyst.
Reported vanadium in the United States Patent (USP) 4098723,4052338, cobalt optionally improves iron-potassium-chromium System Catalyst, pointed out in catalyst, to add the compound of a spot of vanadium and cobalt, not only can improve the stability of catalyst, and improve cinnamic yield.After United States Patent (USP) 4144197 had been reported vanadium, cobalt adding dehydrogenation, its conversion ratio was under 70% situation, and selection of catalysts is about 94%.After European patent EP 5,025 10 is reported in and adds titanium dioxide in iron-potassium-cerium-molybdenum-calcium system, under the situation that keeps high conversion, selectivity increases, under 620 ℃ of temperature, 2.0 water-oil factors, 1.0 air speed conditions, conversion of ethylbenzene reaches 78.37%, the high selectivity 95.19% of styrene.
Chinese patent CN1443738 report adds the nanometer ferro oxide component solution problem that catalyst activity is not high, selectivity is on the low side by adopting in iron-potassium-cerium-molybdenum System Catalyst.Chinese patent CN1470325 has reported and added vanadium, cobalt, manganese, titanium oxide combination in iron-potassium-cerium-molybdenum-calcium system, and these four kinds of oxides have significantly increased selection of catalysts when keeping catalyst activity in optimum addition scope.Chinese patent CN1810367 reported in iron-potassium-cerium-molybdenum-calcium-calcium system adopt potassium oxide in the oxide that adds an amount of niobium, the control catalyst content in the technical scheme below 11%, solved not high, the low problem of selectivity especially of low potassium catalyst activity preferably.Chinese patent CN1810368 has reported to adopt in iron-potassium-cerium-molybdenum system and has added zirconium, tin and at least a technical scheme that is selected from the combination of oxides of calcium, manganese, tungsten, has solved the problem that accessory substance is many, selectivity is low preferably.Chinese patent CN1883796 has reported and has adopted interpolation 0.1～5% to be selected from the technical scheme of oxide at least a among Y, Eu, Gd, Tb, Dy, the Yb in iron-potassium-cerium-molybdenum system, solved catalyst activity preferably, selectivity of styrene is not high enough, the problem that the styrene yield is on the low side.
Summary of the invention
Shortcomings such as it is not high to the objective of the invention is to overcome in the commercial Application catalyst activity, and the styrene yield is not high, selectivity is not high and the life-span is long are at 620 ℃, liquid air speed 1.0h
-1, the water weight of oil is than making ethylbenzene dehydrogenation generate cinnamic conversion ratio 〉=80.20%, selectivity 〉=95.30% under 2.0 the process conditions, obtained performance stable oxide catalyst.
For solving the problems of the technologies described above, the present invention adopts following technical scheme, and a kind of catalyst of efficient ethyl benzene dehydrogenation preparation of styrene is 100 parts in catalyst weight, comprises following component:
A) 35～88 parts ferriferous oxide is with Fe
2O
3Meter;
B) 5～35 parts potassium oxide is with K
2The O meter;
C) 3～20 parts cerium oxide is with Ce
2O
3Meter;
D) 1～10 part molybdenum oxide is with MoO
3Meter;
E) 1～10 part calcium and/or magnesium oxide are respectively in CaO, MgO;
F) 0.1～10 part Cu oxide is in CuO;
G) 0.01～5 part zinc oxide is in ZnO;
H) 0.001～5 part lead oxides is with PbO
2Meter;
I) oxide of 0.001～0.5 part of titanium, zirconium, hafnium, can be wherein one or more, respectively with TiO
2, ZrO
2, H
fO
2Meter;
J) oxide of 0.001～0.5 part of manganese, tin, cobalt, lanthanum, can be wherein one or more, respectively with MnO
2, SnO
2, Co
2O
3, La
2O
3Meter.
Do not get rid of in the catalyst of the present invention and add other catalyst usual auxiliaries.As also adding 1～10 part reinforcing agent in the catalyst, as cement etc.
In above-mentioned each constituent content, iron can iron oxide red and the form of iron oxide yellow add, wherein the weight content ratio of iron oxide red and iron oxide yellow is 0.5～2.5, and optimal proportion is 0.8～1.8, and the total content of iron oxide red and iron oxide yellow is with 50～75 parts of the bests;
Potassium adds K with the form of sylvite
2The content of O is with 8～20 parts of the bests, K
2O content is low excessively, and activity of such catalysts is on the low side, the too high performance that then influences catalyst etc.;
Cerium adds Ce with the form of oxide or salt
2O
3Content with 5～15 parts of the bests, content is low excessively, it is not obvious that catalyst activity improves, too high levels is little to the catalyst performance effect;
Molybdenum adds MoO with the form of oxide or salt
3Content with 3～8 parts of the bests, content is low excessively, it is not obvious that catalyst selectivity improves, too high levels is little to the catalyst performance effect;
Calcium and/or magnesium add with the form of oxide or salt, and the content of CaO and/or MgO can catalytic water gas shift react the knot carbon that reduces catalyst with 1～7 part of the best, makes catalyst obtain higher activity and selectivity;
Copper adds with the form of oxide or salt, and the content of CuO is with 0.1～3 part of the best, and the oxidisability of its metal cation is in Fe
2+With Fe
3+Between, improve the stability of catalyst, thereby improve life of catalyst;
Zinc adds with the form of oxide or salt, and the content of ZnO is that activity of such catalysts promotes auxiliary agent with 0.1～3 part of the best, can improve activity of such catalysts and stability;
Plumbous form with oxide or salt adds PbO
2Content with 0.01～1 part of the best, be the auxiliary agent that promotes the activated centre, content is too low, activity of such catalysts is promoted not obvious, content is too high, cost up;
Copper, zinc and lead all are to add component, in the catalyst of Fe-K-Ce-Mo-Mg (Ca or Mg-Ca) for main body system, synergy between the Cu-Zn-Pb combination of oxides can improve the stability of catalyst significantly, promote the formation of activated centre crystalline phase, be the auxiliary agent that improves catalyst activity and stability, indispensable.
Titanium, zirconium, hafnium add with the form of oxide or salt, are structural promoters, and content is in corresponding oxide, and total addition is with 0.005～0.1 part of the best.Manganese, tin, cobalt, lanthanum add with the form of oxide or salt, are structural promoters, and content is in corresponding oxide, and total addition is with 0.005～0.1 part of the best.
It is the preparation method of dehydrogenation that Preparation of catalysts method of the present invention can adopt conventional iron, as: with catalyst component elder generation dry mixed 0.5～4 hour, adding deionized water mediated 0.5～4 hour, after the moulding, through 60～150 ℃ of dryings, 250～900 ℃ of activation burnings promptly became catalyst of the present invention in 6～18 hours.The drying of catalyst, activation condition adopt method in common, the present invention is not particularly limited, same the present invention is the shape of special defined catalyst not also, recommends catalyst to be preferably extrusion pelletizing moulding, as being the cylindrical catalyst of Φ (2.8～3.3) mm * (5～7) mm.
Catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of the present invention under certain process conditions, also can be used for cumene, p-Methylisopropylbenzene dehydrogenation system isopropenylbenzene and to the methyl isopropyl alkenyl benzene.
The present invention is by adding the Cu-Zn-Pb combination of oxides in the catalyst that for main body is at Fe-K-Ce-Mo-Mg (Ca or Mg-Ca), the oxide of the oxide of at least a titanium of assembly, zirconium, hafnium and at least a manganese, tin, cobalt, lanthanum again, make catalyst by dry mixed, moulding, activation, at 620 ℃, liquid air speed 1.0h
-1, the water weight of oil is than under 2.0 the condition, conversion ratio can reach more than 80.20%, selectivity can reach more than 95.30%, when keeping catalyst activity, has characteristics such as selectivity height, stable height, has solved the problem in the present commercial Application preferably.
Below by embodiment and Comparative Examples the present invention is further set forth.
The specific embodiment
Catalyst carries out activity rating at the isotherm formula fixed bed, and it is as follows to estimate process description:
By the requirement of process conditions, ethylbenzene and water are pumped into blender with metering respectively, enter beds after preheating, vaporization.Product after the dehydrogenation enters cooler through quencher, carries out gas-liquid separation through gas-liquid separator, liquid product through oil water separator with oil and moisture from, with the composition of liquid-phase chromatographic analysis oil phase.Wherein reaction tube is a stainless steel tube, but loading catalyst 100ml.Conversion of ethylbenzene and selectivity of styrene are calculated as follows:
Embodiment 1
With 199.0 gram iron oxide reds, 151.0 gram iron oxide yellow, 88.0 gram potash, 18.0 gram ammonium molybdate, 15.0 gram magnesia, 5.0 gram calcium oxide, 5.0 gram cupric oxide, 2.5 gram zinc oxide, 0.5 gram brown lead oxide, 0.05 gram hafnium oxide, mix after 2 hours 35.0 gram cement adds to do in the kneader, 106.0 gram cerous nitrates and 0.05 gram cobalt nitrate are added wherein after with deionized water dissolving, mediated 2 hours, take out after making material be kneaded into squeezable paste, through extruded moulding, disconnected bar operation, make the cylindrical catalyst of Φ (2.8～3.3) mm * (5～7) mm, drying is 4 hours under 90～120 ℃, place muffle furnace, 300～700 ℃ of calcinings 10 hours, after calcining 4 hours under 770 ℃, naturally cooling obtains finished catalyst and carries out activity rating.The 100ml catalyst is packed in the isothermal boiler tube, at 620 ℃, liquid air speed 1.0h
-1, the water weight of oil is than continuously estimating 1000 hours under 2.0 the condition, initial activity and lifetime results see Table 2 and table 3 respectively.
Embodiment 2
Method by embodiment 1 prepares catalyst, the amount of magnesia, cupric oxide, zinc oxide, brown lead oxide is constant, different is, iron oxide red 184.0 grams, iron oxide yellow 140.0 grams, potash 110.0 grams, cerous nitrate 132.0 grams, ammonium molybdate 24.5 grams, calcium oxide 20.0 grams, titanium dioxide 0.05 gram, manganese dioxide 0.05 gram, cement 20.0 grams, drying is 3 hours under 70～120 ℃, places muffle furnace, 340～800 ℃ of calcinings 7 hours, calcining is after 2 hours down at 800 ℃, and cooling obtains finished catalyst and carries out activity rating naturally.Evaluation method is with embodiment 1, and the initial activity evaluation result of catalyst sees Table 2,1000 hours life tests and shows, as embodiment 1 catalyst, performance is very stable.
Embodiment 3
Method by embodiment 1 prepares catalyst, different is iron oxide red 178.6 grams, iron oxide yellow 203.5 grams, potash 73.4 grams, cerous nitrate 79.4 grams, ammonium molybdate 36.0 grams, magnesium hydroxide 21.8 grams, cupric oxide 2.5 grams, zinc oxide 5.0 grams, brown lead oxide 2.5 grams, zirconium dioxide 0.1, tin ash 0.1 gram, cement 15.0 grams, evaluation method is with embodiment 1, the initial activity evaluation result of catalyst sees Table 2, life test showed in 1000 hours, as embodiment 1 catalyst, catalyst performance stabilised.
Embodiment 4
Method by embodiment 1 prepares catalyst, and different is iron oxide red 148.0 grams, iron oxide yellow 168.6, potash 132.0 grams, ammonium molybdate 18.0 grams, calcium carbonate 35.7 grams, cupric oxide 2.5 grams, zinc oxide 2.5 grams, brown lead oxide 2.0 grams, titanium dioxide 0.1 gram, manganese dioxide 0.1 gram, tin ash 0.1 gram, lanthanum nitrate 0.1 gram (same cobalt nitrate, water-soluble then add again), cement 10.0 grams, in kneader, mediated 3 hours, evaluation method is with embodiment 1, and the initial activity evaluation result of catalyst sees Table 2,1000 hours life tests and shows, as embodiment 1 catalyst, catalyst performance stabilised.
Embodiment 5
Method by embodiment 1 prepares catalyst, different is iron oxide red 189.8 grams, iron oxide yellow 144.2 grams, potash 88.0 grams, cerium oxalate 107.6 grams, ammonium molybdate 30.6 grams, calcium oxide 15.0 grams, magnesium carbonate 3 1.5 grams, cupric oxide 4.0 grams, zinc oxide 4.0 grams, brown lead oxide 4.0 grams, titanium dioxide 0.05 gram, hafnium oxide 0.05 gram, zirconium dioxide 0.05 gram, manganese dioxide 0.05 gram, tin ash 0.05 gram, cobalt nitrate 0.05 gram (water-soluble back adds), lanthanum nitrate 0.05 gram (water-soluble back adds), cement 10.0 grams, evaluation method is with embodiment 1, and the initial activity evaluation result of catalyst sees Table 2,1000 hours life tests and shows, as embodiment 1 catalyst, catalyst performance stabilised.
Embodiment 6
Press the formulation catalyst of embodiment 1, different is that material was done in kneader mixed 2.5 hours, back kneading 1.5 hours is dissolved in water, cylindrical catalyst behind extrusion, disconnected bar is following dry 4 hours at 80～120 ℃, after placing muffle furnace to calcine 4 hours down respectively at 4 hours, 820 ℃ of 580 ℃ of following calcinings, naturally cooling obtains finished catalyst and carries out activity rating.Evaluation method the results are shown in Table 2 with embodiment 1.
The percentage composition of each component tabulation among table 1 embodiment
| Form % | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Fe 2O 3 | 65.00? | 60.00? | 70.00? | 58.00? | 62.00? |
| K 2O | 12.00? | 15.00? | 10.00? | 18.00? | 12.00? |
| Ce 2O 3 | 8.00? | 10.00? | 6.00? | 12.00? | 10.00? |
| MoO 3 | 3.00? | 4.00? | 6.00? | 3.00? | 5.00? |
| CaO? | 1.00? | 4.00? | -? | 4.00? | 3.00? |
| MgO? | 3.00? | 3.00? | 3.00? | -? | 3.00? |
| CuO? | 1.00? | 1.00? | 0.50? | 0.50? | 0.80? |
| ZnO? | 0.50? | 0.50? | 1.00? | 0.50? | 0.80? |
| PbO 2 | 0.10? | 0.10? | 0.50? | 0.40? | 0.80? |
| TiO 2 | -? | 0.01? | -? | 0.02? | 0.01? |
| H fO 2 | 0.01? | -? | -? | -? | 0.01? |
| ZrO 2 | -? | -? | 0.02? | -? | 0.01? |
| MnO 2 | -? | 0.01? | -? | 0.02? | 0.01? |
| Co 2O 3 | 0.01? | -? | -? | -? | 0.01? |
| SnO 2 | -? | -? | 0.02? | 0.02? | 0.01? |
| La 2O 3 | -? | -? | -? | 0.02? | 0.01? |
Comparative example 1
Method according to embodiment 1 prepares catalyst, and different is not add zinc oxide, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
Comparative example 2
Method according to embodiment 2 prepares catalyst, the different cupric oxide that do not add, evaluation method is with embodiment 1, evaluation result sees Table 2.
Comparative example 3
Method according to embodiment 3 prepares catalyst, and different is not add brown lead oxide, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
Comparative example 4
Method according to embodiment 4 prepares catalyst, and different is not add cupric oxide, zinc oxide and brown lead oxide, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
Comparative example 5
Method according to embodiment 5 prepares catalyst, and different is not add ammonium molybdate and cerium oxalate, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
The evaluation result of table 2 embodiment, comparative example gained catalyst
| Example | Reaction temperature (℃) | Liquid air speed (h -1) | Water-oil factor (mass ratio) | Conversion of ethylbenzene % | Selectivity of styrene % | Styrene yield % |
| Embodiment 1 | 620? | 1.0? | 2.0? | 80.65? | 95.32? | 76.88? |
| Embodiment 2 | 620? | 1.0? | 2.0? | 80.36? | 95.51? | 76.75? |
| Embodiment 3 | 620? | 1.0? | 2.0? | 80.41? | 95.78? | 77.02? |
| Embodiment 4 | 620? | 1.0? | 2.0? | 80.28? | 95.62? | 76.76? |
| Embodiment 5 | 620? | 1.0? | 2.0? | 80.92? | 95.37? | 77.17? |
| Embodiment 6 | 620? | 1.0? | 2.0? | 80.82? | 95.34? | 77.05? |
| Comparative example 1 | 620? | 1.0? | 2.0? | 78.49? | 94.82? | 74.42? |
| Comparative example 2 | 620? | 1.0? | 2.0? | 78.26? | 94.77? | 74.17? |
| Comparative example 3 | 620? | 1.0? | 2.0? | 78.08? | 94.32? | 73.65? |
| Comparative example 4 | 620? | 1.0? | 2.0? | 75.29? | 93.63? | 70.49? |
| Comparative example 5 | 620? | 1.0? | 2.0? | 71.28? | 93.59? | 66.71? |
Life of catalyst test data among table 3 embodiment 1
| Evaluation time (hour) | Reaction temperature (℃) | Liquid air speed (h -1)? | Water-oil factor (mass ratio) | Conversion of ethylbenzene % | Selectivity of styrene % | Styrene yield % |
| 100? | 620? | 1.0? | 2.0? | 81.34? | 94.91? | 77.20? |
| 200? | 620? | 1.0? | 2.0? | 81.09? | 95.69? | 77.59? |
| 300? | 620? | 1.0? | 2.0? | 80.49? | 95.88? | 77.17? |
| 400? | 620? | 1.0? | 2.0? | 80.46? | 95.92? | 77.18? |
| 500? | 620? | 1.0? | 2.0? | 80.35? | 95.69? | 76.60? |
| 600? | 620? | 1.0? | 2.0? | 80.78? | 95.50? | 77.14? |
| 700? | 620? | 1.0? | 2.0? | 80.74? | 95.52? | 77.12? |
| 800? | 620? | 1.0? | 2.0? | 81.05? | 95.48? | 77.39? |
| 900? | 620? | 1.0? | 2.0? | 80.98? | 95.51? | 77.34? |
| 1000? | 620? | 1.0? | 2.0? | 80.76? | 95.56? | 77.17? |
Claims (15)
1. the catalyst of an ethyl benzene dehydrogenation preparation of styrene is characterized in that in catalyst weight be 100 parts, is made up of following component:
A) 35～88 parts ferriferous oxide is with Fe
2O
3Meter;
B) 5～35 parts potassium oxide is with K
2The O meter;
C) 3～20 parts cerium oxide is with Ce
2O
3Meter;
D) 1～10 part molybdenum oxide is with MoO
3Meter;
E) 1～10 part calcium and/or magnesium oxide are respectively in CaO, MgO;
F) 0.1～10 part Cu oxide is in CuO;
G) 0.01～5 part zinc oxide is in ZnO;
H) 0.001～5 part lead oxides is with PbO
2Meter;
I) one or more in the oxide of 0.001～0.5 part of titanium, zirconium, hafnium are respectively with TiO
2, ZrO
2, H
fO
2Meter;
J) one or more in the oxide of 0.001～0.5 part of manganese, tin, cobalt, lanthanum are respectively with MnO
2, SnO
2, Co
2O
3, La
2O
3Meter;
K) 1～10 part reinforcing agent.
2. catalyst according to claim 1 is characterized in that ferriferous oxide adds with the form of iron oxide red and iron oxide yellow.
3. catalyst according to claim 2, the weight content ratio that it is characterized in that iron oxide red and iron oxide yellow is 0.5～2.5.
4. catalyst according to claim 2, the weight content ratio that it is characterized in that iron oxide red and iron oxide yellow is 0.8～1.8.
5. catalyst according to claim 2, the total content that it is characterized in that iron oxide red and iron oxide yellow is 50～75 parts.
6. catalyst according to claim 1 is characterized in that K in the catalyst
2The content of O is 8～20 parts.
7. catalyst according to claim 1 is characterized in that Ce in the catalyst
2O
3Content be 5～15 parts.
8. catalyst according to claim 1 is characterized in that MoO in the catalyst
3Content be 3～8 parts.
9. catalyst according to claim 1 is characterized in that the content of CaO in the catalyst and/or MgO is 1～7 part.
10. catalyst according to claim 1, the content that it is characterized in that CuO in the catalyst is 0.1～3 part.
11. catalyst according to claim 1, the content that it is characterized in that ZnO in the catalyst is 0.1～3 part.
12. catalyst according to claim 1 is characterized in that PbO in the catalyst
2Content be 0.01～1 part.
13. catalyst according to claim 1, the total content that it is characterized in that titanium in the catalyst, zirconium, hafnium in corresponding oxide, are 0.005～0.1 part.
14. catalyst according to claim 1, the total content that it is characterized in that manganese in the catalyst, tin, cobalt, lanthanum in corresponding oxide, are 0.005～0.1 part.
15. described Preparation of catalysts method of claim 1, it is characterized in that catalyst component elder generation dry mixed 0.5～4 hour is added deionized water and mediated 0.5～4 hour, after the moulding, through 60～150 ℃ of dryings, 250～900 ℃ of activation burnings promptly became catalyst in 6～18 hours.
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| RU2803808C2 (en) * | 2018-12-20 | 2023-09-20 | Чайна Петролеум Энд Кемикал Корпорейшн | STRUCTURED MONOLITHIC CATALYST FOR REDUCING NOx EMISSIONS IN EXHAUST GAS COMPOSITION, METHOD FOR PRODUCING CATALYST AND ITS APPLICATION |
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| CN102343269B (en) * | 2010-08-05 | 2013-07-31 | 中国石油天然气股份有限公司 | Ethylbenzene dehydrogenation catalyst taking micron-sized ferric oxide and potassium carbonate as raw materials |
| IN2014CN04377A (en) * | 2011-12-22 | 2015-09-04 | Basf Se | |
| CN103769142A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing phenethylene through ethylbenzene dehydrogenation |
| CN105312059B (en) * | 2014-07-24 | 2018-02-13 | 中国石油化工股份有限公司 | The catalyst of dehydrogenation of ethylbenzene to styrene |
| CN105777480B (en) * | 2014-12-15 | 2018-10-16 | 中国石油天然气股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN105749934B (en) * | 2014-12-15 | 2018-12-28 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation with low water ratio and preparation method thereof |
| CN106582685B (en) * | 2015-10-16 | 2019-04-12 | 中国石油化工股份有限公司 | Low-temperature ethyl benzene dehydrogenation catalyst and preparation method thereof |
| CN107304159B (en) * | 2016-04-25 | 2021-03-26 | 曹炳铖 | Method for preparing methyl styrene and coproducing mesitylene by dehydrogenation of carbon nonaarene mixture and alkyl arene dehydrogenation catalyst |
| EP3962643A4 (en) * | 2019-05-03 | 2023-01-11 | Golu Hydrogen Technologies Inc. | Catalysts for hydrogen production |
| CN116924796B (en) * | 2023-08-14 | 2024-05-14 | 昆明理工大学 | ABO (anaerobic-anoxic-oxic)3Low dielectric loss ceramic and preparation method thereof |
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