CN1016165B - Catalyst rich in macropores for selective hydrogenation of olefins - Google Patents
Catalyst rich in macropores for selective hydrogenation of olefinsInfo
- Publication number
- CN1016165B CN1016165B CN 87106441 CN87106441A CN1016165B CN 1016165 B CN1016165 B CN 1016165B CN 87106441 CN87106441 CN 87106441 CN 87106441 A CN87106441 A CN 87106441A CN 1016165 B CN1016165 B CN 1016165B
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- pore volume
- catalyst
- alumina
- dusts
- Prior art date
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- Expired
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- 239000003054 catalyst Substances 0.000 title abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title description 23
- 150000001336 alkenes Chemical class 0.000 title description 8
- 239000011148 porous material Substances 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 41
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 34
- 230000032683 aging Effects 0.000 description 17
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000006187 pill Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 sulphur compound Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- MERBOASPEBJVLI-UHFFFAOYSA-N trialuminum oxygen(2-) Chemical compound [O--].[O--].[O--].[Al+3].[Al+3].[Al+3] MERBOASPEBJVLI-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A catalyst for selectively hydrogenating nonconjugated diolefins to monoolefins comprises nickel and sulfur deposited on the surface of a macroporous alumina support. Preferably, the catalyst does not contain halogens, noble metals, alkaline earth metals or alkali metals. The catalyst is characterized by a very low percentage of the total pore volume of the pore surface having an average pore diameter of less than 150 angstroms, the largest portion of the pore volume being in the form of macropores having a pore diameter of 500 to 1500 angstroms.
Description
The present invention relates to generally be used for the catalyst composition of hydrocarbon conversion process, the present invention directly relates to the composition that is used for diolefine is converted to the solid catalyst of monoolefine.Said composition can be used to handle the technological process that butene feedstock stream makes it to be transformed into motor spirit, and the concentration that can be used for reducing the diolefine that generates owing to dehydrogenation reaction in the product flow.The present invention be more particularly directed to selective hydrogenation catalyst, this catalyzer is made up of alumina base or upholder basically.This upholder has unique vesicular structure, and nickel or sulphur deposition is arranged on this upholder.
As everyone knows, in petroleum chemistry and rendering industry, wish that sometimes changing diolefine selectively becomes monoolefine.This conversion advantage has economically promoted to be used in a large number this purpose Study of Catalyst.Many these type of catalyzer are used for solid-state upholder such as aluminum oxide to traditional hydrogenation catalyst metal such as nickel, platinum and palladium.For instance, United States Patent (USP) 3,234,298(orchid top grade (Langhout etal) has suddenly been narrated and uses the catalyzer of nickelous sulfide on aluminum oxide to come that the cracking hydrocarbon ils that contains diene is carried out selective hydrogenation to handle.United States Patent (USP) 3,472, (Cosyns etal) such as 763(Coases) a kind of selective hydrogenation catalyst described, this catalyzer is by the nickel that contains percent 1 to 20 on the aluminum oxide as selective hydrogenation catalyst, and it exists as the form of nickel oxide.This reference is pointed out, preferably uses this catalyzer of sulphur compound pre-treatment, and points out preferable hole pore size distribution.
United States Patent (USP) 3,662, No. 015 (weighing apparatus pine etc. (Komatsu etal) have been narrated the selective hydrogenation catalyst of a kind of nickel on aluminum oxide.United States Patent (USP) 4,440, No. 956 (Kao Weilin (Couvillion) relates to a kind of such catalyzer, and it can be with the acetylene class that removes in the liquid hydrocarbons flow that contains diolefine, and does not reduce the per-cent of diolefine in this raw material basically.Known this reference has proposed multiple aluminum oxide, and these aluminum oxide can combine with hydrogenation metal commonly used, to be used for making this class catalysts selective.United States Patent (USP) 3,919, No. 341 (looking into graceful grade (Germanas et al)) narrated the composition of a kind of nickelous sulfide on aluminum oxide, and said composition can be used as the catalyzer of isomerisation of olefin basically.But, by can determine that referring to chart 2 and the 12nd column the test-results of reporting has shown the selective hydrogenation effect of divinyl in chart.
At last, known United States Patent (USP) 4,469, No. 907 (Alan's shells etc. (Araki et al)) have narrated a kind of modification method of selective hydrogenation, United States Patent (USP) 3,696, No. 160 (Qiao Mei (Chmyn)) narrated a kind of perfect method, utilizes exactly in the upstream process of alkylation process or the selective hydrogenation effect that combines with alkylation process.In this alkylation process, C
3And C
4Alkene is consumed to produce motor spirit.
United States Patent (USP) 4,179, No. 408 (Sang Qiesi etc. (Sanchez et al)) have described the preparation method of spherical alumina catalyst support, and the aperture accounts for the major part of total pore size volume on this upholder greater than the macropore of 1000 dusts (column 20-22).United States Patent (USP) 4,179, No. 411 (Brosman (Bruersma)) also described a kind of aluminum oxide with specific pore size distribution.
The present invention relates to a kind of catalytic composition of uniqueness, the utmost point is suitable for the selective hydrogenation effect from the diolefine to the monoolefine.This catalyzer has good especially selectivity when conversion has the diolefine of 8 above carbon atoms, thereby increases the productive rate of monoolefine in the product stream.The salic upholder of this catalyst pack, about 4.1 to 25%(weight) nickel and about 0.05 to 1.5%(weight) sulphur.Be preferably, this catalyzer is substantially devoid of halogen and precious metal.This catalyzer is characterised in that its seldom micropore and have abundant macropore.Therefore, bore dia less than the hole of 150 dusts less than percent 25 of catalyzer total pore size volume, bore dia greater than the hole of 600 dusts then more than percent 60.
Fig. 1 is a graphic representation, and it provides the volume percent of diolefine in replica plant's effluent liquid that this catalyzer and two kinds are tested with reference to catalyzer.
Fig. 2 is a similar graphic representation, and it has provided the concentration of the contained monoolefine of in same process of the test effluent liquid.
Monoolefine is produced or consumed to many petroleum technology flow processs. In many these class technological processes, alkadienes is regarded as impurity. For example, in the production of the linear alkylbenzene (LAB) of composite technology flow process (as United States Patent (USP) 3,484, No. 498 described), monoolefine produces in the deoxidation section, enters then the alkylation section. Wherein, alkene and benzene reaction produce the linear alkyl aromatic hydrocarbons product. Producing alkadienes in dehydrogenation section is that inevitably these alkadienes are present in the alkene that enters the alkylation section usually to a certain extent. The existence of straight chain diene thing has caused the generation of undesirable byproduct such as various biphenol compounds. These impurity have added to required linear alkylbenzene (LAB) product to undesirable characteristic. The existence of alkadienes has caused the generation of unwanted high boiling byproduct, and has increased sour consumption rate. If alkadienes is regarded as monoolefine and paraffins mixture or the inapt component in the pure olefin stream basically, then selective hydrocatalyst of the present invention is applied to just can remedy above-mentioned situation in the part flow process. Catalyst of the present invention also can be used for the purifying step of efflux in the separation of olefins flow process, and this separation process refers to such as passing through application choice absorption techniques, the flow process of the separation of olefins from alkene and paraffins mixture.
Therefore, Catalyst Design of the present invention is used for diolefine is selectively hydrogenated into monoolefine, and this catalyzer comprises a kind of alumina supports, and this upholder contains about 0.05 to 1.5%(weight) sulphur and about 1.0 to 25%(weight) nickel.This alumina supports is characterised in that its total pore size volume greater than 1.4cc/g but less than 3cc/g, and its surface-area is greater than 150m
2/ g, its median pore diameter less than the hole of 150 dusts less than percent 25 of total pore size volume, bore dia greater than the hole of 600 dusts more than percent 60.
Use the feedstream of this catalyzer can comprise that per molecule has the mixture of the different hydrocarbon of same carbon atoms number, or the mixture of the hydrocarbon of suitable scope carbonatoms is arranged.For example, use the feedstream of this catalyzer, can be and only contain C basically
4Or C
5Hydrocarbon.In addition, feedstream can comprise C
8To C
15The mixture of hydrocarbon, in this class hydrocarbon, comprise alkane, monoolefine and diolefine.Usually, can believe that this catalyzer will be very effective when the processing per molecule has the hydrocarbon of 8 to 20 carbon atoms.
Selective hydrogenation process is being operated under the demulcent hydroconversion condition usually relatively.These conditions cause these hydrocarbon to be in liquid state usually.Usually reactant is maintained at that only to be enough to keep itself be under the minimum pressure of liquid hydrocarbon.Broad, suitable working pressure scope is about 40 to 800 pounds/inch
2(276-5516KPag), preferable pressure range is about 50 to 300 pounds/inch
2(345-2069KPag).Suitable relatively temperature range is about 25 to 300 ℃ (77-662).Preferable hydrogenation section temperature maintenance (122-390) between about 50 and 200 ℃.Reactant should be greater than 1 hour by the liquid hourly space velocity of selective hydrogenation catalyst
-1Speed should be greater than 5 hours preferably
-1, and preferably at 5 and 35 hours
-1Between.Another variable operational condition is the hydrogen kept in the selective hydrogenation section and the ratio of diolefine.For obtaining the molecular weight that the amount of to a certain degree changing required hydrogen is considered to depend on temperature of reactor and raw material hydrocarbon.For the monoolefine of avoiding a great deal of reaches unwanted saturated, when the diolefine in the liquid phase process logistics was selectively hydrogenated into monoolefine, the amount of used hydrogen should be less than the calculated value of 2 times required hydrogen.Preferably, hydrogen and the mol ratio that enters the diolefine in the selective hydrogenation catalytic bed material maintain between 1: 1 and 1.8: 1.
In some cases, may under the condition of the calculated value that is lower than required hydrogen, operate, mol ratio was not less than 0.75: 1st, acceptable.Certainly, top condition will depend on composition and the desired factors such as diolefine degree of saturation that reach such as feedstream.
This catalyzer is preferably in the fixed-bed reactor that include cylindric catalytic bed and uses, and reactant moves with vertical direction in this catalytic bed.Be preferably and allow reactant upwards flow through reactor, can cause good mixing like this.This catalyzer can be in reactor exists with ball shape, spherical, extruding strip, anomocytic type particle etc.For using this catalyzer, be preferably reactant is heated to required conversion zone temperature in, then mix with hydrogen, pass through reactor then.Another kind method is that reactant mixes with the hydrogen of aequum, is heated to required temperature in then.In either case, the liquid stream of conversion zone can pass through a product retrieving arrangement, to remove remaining hydrogen, perhaps, and if the existence of remaining hydrogen is the acceptable words, the product utilization section that can directly enter the downstream.Hydrogen can by with this effluent liquid flash distillation to low pressure or this effluent liquid is sent into washing tower remove.
The catalyzer of preferred shape is to have the sphere of diameter between about 1/64 to 1/4 inch (0.4-6.4mm).Globular solid catalyst upholder can comprise spreading and mold pressing by the several different methods manufacturing.But being more preferably this spherical alumina particle makes by the method for alumina sol gelation.This method can be referring to United States Patent (USP) 2,620, No. 314 (He Kece (Hoekstra)).Thisly make aluminum oxide generation gelling, in the present technique field, be called drop method usually to form the globular method.Alumina sol also can be by multiple diverse ways preparation.A kind of typical method is with the aqueous hydrochloric acid dissolved aluminum metal that is about 12%, to produce aluminum chloride colloidal sol.Another kind method is included in electrolytic chlorination aluminum solutions in the electrolyzer.The common method of preparation alumina sol is that aluminum metal is added in the aluminum chloride aqueous solution, dissolves with this mixture heating up and under boiling point then.These method for makings of alumina sol are not limited to feature of the present invention.And this colloidal sol can be produced by any method that obtains suitable sol.Be preferably, this colloidal sol can have about 13: 1 or the above aluminium and the weight ratio of chlorine.
A kind of method preferably of this colloidal sol generation agglomerative is comprised: being lower than under the gelation temperature, this colloidal sol is mixed with jelling agent, in hot oil bath, the gained mixture is dispersed into droplet then, thereby pectisation takes place, form solid spherical gel particle.This alumina hydrogel ball is handled through certain ageing, to obtain required physical properties.A common complete ageing is handled and was included in the deep fat ageing at least 10 hours, and ageing is at least 10 hours in suitable liquid alkaline medium, washes with water at last, to reduce the concentration of alkaline medium.In this alumina particle moulding and ageing flow process, when this water-setting capsule and pill in liquid alkaline medium before the ageing, the contact of discord water.This pill is water miscible at the commitment of this flow process, so can be destroyed because of contacting with water.Carry out between the about 49-260 of temperature ℃ (120-500) of this ageing processing, and should be more than 100 ℃ (212 °F).Existing tendency is to allow gas overflow rapidly, and these gases can make the hydrogel pill break or make its weakened.In moulding and aging step,, when ageing, can use higher temperature by keeping high pressure.Adopt high temperature that more such advantages are provided, as remove the ageing in liquid basic solution from.Thereby this pill can directly wash with water after oily aging step.Be typically, about 1 to 24 hour of the particle of gelationization ageing in oil bath, the ageing temperature is about 90-150 ℃ (194-302 °F), and pressure range is with 1 normal atmosphere to 150 pound/inch
2(1034K Pag).If under atmospheric pressure through oily ageing, the ageing 2 to 4 hours again in rare ammonia soln usually of the particle of this gelationization.After the ageing, these particles are through washing, drying and roasting.
The gelationization of alumina hydrosol can be undertaken by this colloidal sol is mixed with vulkacit H (HMT).Vulkacit H is a weak base, is about at 4 to 10 o'clock at pH and has very strong shock absorption.This material is when temperature increases, and hydrolysis rate also increases, and evolving gas suddenly not, this is an advantage in gelatinization process.As everyone knows, the mixture of urea and HMT can be used as jelling agent.To higher temperature, this jelling agent decomposes and generation ammonia this mixture heating up.Ammonia causes that this water-sol changes into gel, and makes it to form the alumina hydrogel pill.After gelationization and the ageing, these particles are heated to about 650 ℃ (1202 °F) then gradually in baking oven inherent 110 ℃ (230) oven dry down, and roasting 2 hours in air and under the uniform temp.The material that obtains behind the air roasting is gama-alumina basically." basically " meaning of a speech is, the alumina supporter that obtains comprises 90%(weight at least) gama-alumina.For guaranteeing that carrier substance is gama-alumina basically, this carrier substance is to be exposed to 850 ℃ (1562) above temperature.Be exposed to the transformation mutually that 850 ℃ of (1562) above temperature can cause aluminum oxide, this can make this aluminum oxide from γ be transformed into δ-, θ-even may be transformed into Alpha-alumina.This transformation mutually follows subsiding of aperture (less than 100 dusts) usually, produces big hole, and the result causes the increase of total pore volume.But because surface-area is directly proportional with the aperture and the quantity of aperture, subsiding of these holes caused the surface-area of this carrier substance to reduce in a large number.Therefore, by utilizing drop method, might form the gamma-aluminium oxide carrier material, its total pore volume is greater than 1.4cc/g, and surface-area surpasses 150m
2/ g has avoided the problem that other forming techniques recited above brought.
Although not clear fully as yet, adopt the alumina supporter material of drop method preparation, produced than with the technology known in the other technologies field as superior many of the carrier that is crushed to.Have been found that the alumina supporter of making has the required total pore volume greater than 1.4cc/g when adopting drop method, and keep greater than 150m
2The high surface area of/g.Other forming techniques are unaccommodated, because for total pore volume is increased, this carrier must be through heat treated, as roasting.But this processing causes the rapid decline of carrier surface area, relatively is typically, and these carriers that make with non-oil drop method can not obtain the total pore volume greater than 1.0cc/g.
About produce the narration of aluminum oxide pill preferably with oil drop method, can be referring to United States Patent (USP) 3,096, No. 295,3,926, No. 849 and 4,250, No. 058, these patents are hereby incorporated by reference document.Spherical alumina particulate preparation is also at United States Patent (USP) 4,179, No. 408,4,179, No. 411 and 4,514, narrates to some extent in No. 511.
Except basic alumina supporter material, also having two components is important component in this catalyzer.At first be the nickel component, it may only be present in the outside surface of alumina supporter material, or is scattered in equably in the whole carrier.The outside surface of carrier has nickel, and its meaning is meant that nickel is surface deposition, and promptly the nickel on all carriers is to concentrate in the thin layer of 200 microns of carrier outermosts basically.Nickel concentration in the finished catalyst better is in 1 to 25%(weight) between, preferably 5 and 15%(weight) between, its weight percent is pressed metal element and is calculated.If necessary, the nickel component can add in the catalyzer in the pill forming process.But, be preferably by the dipping nickel component of catalyzer is joined in the established aluminum oxide pill.Described dipping is exactly that established aluminum oxide pill is immersed in the solution of nickel compound.Be preferably established, immerse in the solution of nickelous nitrate, nickelous chloride, single nickel salt or nickel acetate or other water-soluble nickel compound through the aluminum oxide pill of roasting.Be preferably then and use the rotation steam vaporizer, pill with solution evaporation fall, until reaching dry.Dry granules can be cured 1 hour under the temperature of about 150 ℃ (302), then about 525 ℃ (977) following roasting 1 hour.Then, the pill of formation can be used nitrogen drying and purge, and preferably contacts with hydrogen-containing gas, experiences a reduction step.
The sulphur component that is preferably catalyzer equally exists only in the surface of alumina supporter with main amount.This component concentrations is preferably in about 0.05 to 1.5%(weight) between change, the preferred range of sulphur concentration is from 0.1 to 1.0%(weight on this catalyzer), the sulphur concentration that best is in finished catalyst is less than 0.5%(weight).Be preferably, alumina supporter form and nickel deposition to this alumina supporter material after, ability is added to the sulphur component on this catalytic composition in last preparation process.In this vulcanisation step, the cure conditions that composition originally will stand should be enough to the sulphur concentration that provides required.Sulfuration can be carried out under liquid-phase condition, carries out but be preferably in gas phase.Thereby preferably contact with originally composition with the gasiform sulfocompound, the sulphur component is deposited on the catalyzer.Be preferably this sulfocompound and be mixed with hydrogen.A kind of preferable sulfur-bearing or product sulphur compound are hydrogen sulfide.Other can be used for the sulfur-bearing of this purpose or produce sulphur compound comprising ammonium sulfide, sulphur hydrogenation ammonium, alkyl and aryl mercaptan, organic thioether, disulphide, thioaldehydes and other product sulphur compounds.Thereby preferable cure conditions comprises that it is gaseous state that temperature of reaction should be enough to keep the sulfuration compound, and its variation range is about 10 to 500 ℃ (50-932 °F).If use hydrogen sulfide to make vulcanizing agent, then temperature range is about 20 to 400 ℃ (68-752 °F) preferably.The used pressure of vulcanisation step can be in very wide scope, because of pressure does not have a significant impact sulfidation.The employing normal atmosphere is relatively good.Composition available hydrogen-hydrogen sulfide originally vulcanizes statically, or sulfuration in containing the flowing gas stream of about 5 to 30% hydrogen sulfide, and this gas stream is with about 2.5 to 10 the gaseous state hourly space velocity catalyzer by originally.
The characteristics of the preferred embodiment of catalyzer of the present invention are that also those had better not be present in the compound in the catalytic composition.Therefore this catalyzer can be summarized as " being substantially free of " some element.It is to want to show without any intention to be included in a specific element or a group element in the catalyzer especially that term herein " is substantially free of ".But, will be appreciated that, owing in the chemical preparations of technical grade, contain impurity, and because catalyzer manufactory is used to produce various catalytic composition, thereby might pollute in the mill, and some not need material will be inevitable to the pollution of catalyzer.Term " is substantially free of " at this and is not used for showing do not have an element-specific or a group element fully, and is meant the 0.1%(weight of the concentration of a element that this is specific or a group element less than the finished catalyst total amount).
Be preferably this catalyzer and be substantially free of precious metal or platinum metals, comprising platinum, palladium, rhodium and iridium.Be preferably this catalyzer and be substantially free of group VIII metal except that nickel.Therefore this catalyzer is substantially free of iron and cobalt.In addition, this catalytic composition preferably is substantially free of alkaline-earth metal, and wherein modal is calcium, strontium and barium.This catalyzer also should be substantially free of basic metal, and wherein lithium, sodium and potassium are the most frequently used catalyst component, and last, this catalytic composition preferably also is substantially free of the halogen that comprises fluorine, chlorine, bromine and iodine.
One the feature of this catalytic composition is the selective hydrogenation catalyst that can be used as diolefine, and it is substantially free of halogen and precious metal.This catalyzer comprises a kind of alumina supporter material, has greater than 150m
2Less than 25% of catalyzer total pore volume, mean pore size surpasses 60% of total pore volume greater than the hole of 600 dusts, also comprises 1 to 25%(weight simultaneously less than the hole of 300 dusts for the total surface area of/g, mean pore size) nickel and 0.1 to 1%(weight) sulphur.
The high-performance of this catalyzer can be found out from the data Fig. 1 and Fig. 2.Data among these figure are under same replica plant and the same terms, three kinds of different catalyzer are tested obtain, in order that determine the effect of these catalyzer to the diolefine selective hydrogenation, these diolefine are present in the feedstream that comprises paraffinic hydrocarbons and diolefine mixture.This kind feedstream it is believed that be represent those with dehydrogenating technologies of industry from by C
10To C
13The prepared hydro carbons of feedstream that hydrocarbon is formed.This feedstream comprises the aromatic hydrocarbons of about 0.99% volume, and the aliphatic hydrocarbon moiety in the feedstream comprises about 0.1%(volume) C
9, the 11.2%(volume) C
10, the 26.5%(volume) C
11, the 34.5%(volume) C
12, the 27.6%(volume) C
13With the 0.1%(volume) C
14This feedstream contains 85.46% saturates, 11.46% monoolefine and 2.09% diolefine.The rest part of feedstream is made up of unconventional hydrocarbon.Feedstream leaves in earlier in the head tank of the highly purified nitrogen atmosphere with pressurization, till this stock liquid is saturated by hydrogen.In test, feedstream is with 5m
-1Liquid hourly space velocity and the contact of different catalyzer, used temperature is 200 ℃ (392 °F), pressure is 100 pounds/inch
2(689KPag).The liquid stream sampling regularly of replica plant is also analyzed, so that the point data on Fig. 1 and Fig. 2 to be provided.Should be noted that the logistics time that figure upper edge X-axis or X-coordinate are painted is the time of actual measurement, is catalyzer by logistics by measuring after 552 hours altogether.
The composition of above-mentioned three kinds of catalyzer testing in experiment is listed in the following table.Catalyst A is corresponding to the preferable catalytic composition of the present invention.Catalyst B is a kind of catalyzer of alumina base, and it comprises a carrier substance, makes with preferable drop method too.Catalyzer C is a kind of carrier substance of extrusion pressing type, and this material contains the mixture of the clay of the aluminum oxide of 80% weight and 15% weight.As shown in Figure 1, handle the hydrocarbon liquid stream that produces, have than catalyst B and the low diene concentration of C through the preferable catalytic composition of catalyst A.Catalyst B contains the nickel of same amount with C and has vulcanized with identical method.But the more important thing is the information that to notice that Fig. 2 provides.This figure shows that catalytic composition of the present invention has better effect than those two kinds of comparative catalysts when producing the monoolefine of required higher concentration.By the information that relatively provides, can find that compare with C with catalyst B, catalyst A can more only play hydrogenation to diolefine selectively by Fig. 1 and Fig. 2.Can find out obviously that from the result catalyst B and C also play hydrogenation to the monoolefine that is present in the feedstream simultaneously except diolefine is risen the hydrogenation.Therefore clearly, adopt the technology of catalyst A can obtain the required product of high yield, no matter this product only is a monoolefine, still consumes monoolefine and the product as the alkylation process of producing linear alkylbenzene that makes.
Referring to following table as can be seen, this catalyst composition of catalyst A is very unique on its pore size distribution.Especially fine porosity (＜300 dust) to account for the per-cent of total pore volume very low, macrovoid (＞600 dust) provides most pore volume.Can find that most macrovoid volume is to be provided by the hole of aperture less than 1500 dusts.By contrast, reference catalyst has the pore volume of big per-cent from aperture.The total pore volume of preferred catalysts of the present invention is more much bigger than the total pore volume of reference catalyst.
Finished catalyst of the present invention should have the cumulative volume greater than 1.4cc/g.Be preferably that this catalyzer can have greater than 1.4cc/g but less than the pore volume of 3cc/g.As previously mentioned, be less than 25% pore volume, better be less than 20%, be to provide by the hole of mean pore size less than 150 dusts, used measuring method is a mercury immersion method, the a large amount of macrovoid of preferential selection, requiring that the pore volume more than 60% is arranged is to be provided by the hole of mean pore size greater than 600 dusts, it is undesirable providing the pore volume of this quantity by some king-sized holes.On the contrary, the macroporous pore size distribution of this catalyzer has the hole of aperture between 600 and 1500 dusts and should account for 50% of total pore volume at least with narrower relatively good, is more preferably these holes and accounts for 60% of total pore volume.
Table
Catalyst A B C
Carrier compositions aluminum oxide aluminum oxide aluminum oxide+clay
Ni% weight 9.5 9.9 9.6
S% weight 0.27 0.10 0.22
Surface-area m
2/ g 174 195 262
Total pore volume cc/g 1.63 0.732 0.882
The pore volume of various holes
%
＞1500 dusts 1.47 0.34 20.0
＞1000 dusts 46.2 0.34 22.1
＞600 dusts 65.9 1.16 24.5
＞500 dusts 67.3 1.38 25.4
＞300 dusts 79.0 2.9 29.9
＞150 dusts 85.5 26.0 43.6
Claims (6)
1, a kind of catalyzer that is used for diene directly is selectively hydrogenated into monoolefine, the alumina supporter material that comprises the nickel of the sulphur that contains 0.05 to 1.5% weight and about 1.0 to 25% weight, the feature of this alumina supporter material is that total pore volume is greater than 1.4 but less than 3cc/g, surface-area is greater than 150m
2/ g, and the pore volume that only is less than total pore volume 25% provides by the hole of aperture less than 150 dusts, more than the pore volume of total pore volume 60% from the hole of aperture greater than 600 dusts.
2, according to the catalyzer of claim 1, it is characterized in that, is to be provided by the hole of mean pore size less than 300 dusts less than the pore volume of total pore volume 25%.
3, according to the catalyzer of claim 1, it is characterized in that, account for the pore volume of total pore volume 50% at least, with providing by the macropore of mean pore size between 600 to 1500 dusts.
4, according to the catalyzer of claim 1, wherein this alumina supporter material carries out gelling with alumina sol and prepares.
According to the catalyzer of claim 4, it is characterized in that 5, the gelling of this alumina sol is undertaken by drop method.
According to the catalyzer of claim 1, it is characterized in that 6, this alumina supporter material is gama-alumina basically.
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| CN 87106441 CN1016165B (en) | 1987-09-21 | 1987-09-21 | Catalyst rich in macropores for selective hydrogenation of olefins |
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|---|---|---|---|
| CN 87106441 CN1016165B (en) | 1987-09-21 | 1987-09-21 | Catalyst rich in macropores for selective hydrogenation of olefins |
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| CN1016165B true CN1016165B (en) | 1992-04-08 |
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| FR2689517B1 (en) * | 1992-04-02 | 1995-07-28 | Inst Francais Du Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF HYDROCARBONS. |
| US8232431B2 (en) | 2008-09-22 | 2012-07-31 | The Procter & Gamble Company | Specific branched surfactants and consumer products |
| US7994369B2 (en) | 2008-09-22 | 2011-08-09 | The Procter & Gamble Company | Specific polybranched polyaldehydes, polyalcohols, and surfactants, and consumer products based thereon |
| US8193111B2 (en) * | 2009-07-24 | 2012-06-05 | Uop Llc | Process or system for desorbing an adsorbent bed |
| BR112013019685A2 (en) | 2011-02-17 | 2016-10-18 | Procter & Gamble | compositions comprising mixtures of c10 -C13 alkyl phenyl sulfonates |
| US20120213726A1 (en) | 2011-02-17 | 2012-08-23 | Phillip Richard Green | Bio-based linear alkylphenyl sulfonates |
| DE102012212317A1 (en) * | 2012-07-13 | 2014-01-16 | Evonik Industries Ag | Thioetherification of mercaptans in C4-hydrocarbon mixtures |
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