CN1181165C - Selective hydrogenation catalyst - Google Patents
Selective hydrogenation catalyst Download PDFInfo
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- CN1181165C CN1181165C CNB011428384A CN01142838A CN1181165C CN 1181165 C CN1181165 C CN 1181165C CN B011428384 A CNB011428384 A CN B011428384A CN 01142838 A CN01142838 A CN 01142838A CN 1181165 C CN1181165 C CN 1181165C
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- carrier
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- palladium
- selective hydrogenation
- heavy
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000001035 drying Methods 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
- 239000000969 carrier Substances 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract 1
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- 150000001993 dienes Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl alkenyl arene Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 241000143437 Aciculosporium take Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000006028 Sambucus nigra Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a selective hydrogenation catalyst, which is prepared from 0.15 to 0.5 wt% of palladium, 0.1 to 3.0 wt% of alkali-earth oxide, and carriers (Al2O3), wherein the specific surface of the carriers (Al2O3) is from 50 to 150m<2>/g, the specific pore volume is from 0.35 to 0.55 ml/g, and pores whose radii are from 5.0 to 10.0 nm account for more than 70% of the total pore volume. Firstly, the surfaces of the carriers are modified by the alkali-earth oxide, and then the palladium (active components) is loaded on the carriers. The catalyst is suitable for a section of selective hydrogenation process of cracking gasoline, and is suitable for a monoolefin generating process by the selective hydrogenation of the crown unsaturated hydrocarbon of C<3-6> distillate oil.
Description
1. technical field
The present invention relates to a kind of selective hydrogenation catalyst, specifically, is a kind of one-stage selective hydrogenation of gasoline splitting catalyzer, or C
3-6Distillate camber unsaturated hydrocarbons selective hydrogenation catalyst.
2. background technology
As everyone knows, under the condition that steam exists, hydrocarbon gas or liquid hydrocarbon Pintsch process are produced in the process of ethene and propylene, and pyrolysis gasoline obtains as by product.Except that containing benzene,toluene,xylene, also contain the hydro carbons of unsaturated and easy oxidation in various degree in the pyrolysis gasoline, generate the gelationus compound as easy polymerization reaction take place such as diolefine and alkyl alkenyl arene, thereby pyrolysis gasoline can't directly be used.Industrial common elder generation is with the C in the pyrolysis gasoline
5, C
9After the cut excision, to middle cut (C
6-C
8) adopt the method for two-stage hydrogenation to carry out processing treatment.One-stage selective hydrogenation mainly is to make diolefin and alkyl alkenyl arene component generate corresponding alkene and alkylaromatic hydrocarbon, again through secondary hydrogenation, removes monoolefine, and after making the organic compound hydrogenation decomposition and separation of sulfur-bearing, nitrogen, oxygen and chlorine, makes aromatics extraction raw material.At present the one-stage selective hydrogenation of gasoline splitting catalyzer that uses in the industrial production mainly contains two classes, is respectively active ingredient with nickel and is active ingredient with the palladium, it is carried on aluminum oxide or is on the carrier of major constituent with the aluminum oxide.Two class catalyzer respectively have characteristics, the temperature of reaction height of nickel catalyst, and the height unsaturated hydrocarbons easily generates colloid, thereby the regeneration period is short, needs frequent regeneration, but the low price of catalyzer; Palladium series catalyst is active high, and selectivity is good, and temperature of reaction is low, and the regeneration period is long, but the cost of catalyzer is higher.What use was more on the present industrial production is the precious metal palladium series catalysts.
CN 1071443A discloses a kind of one-stage selective hydrogenation of gasoline splitting catalyzer, is used for pyrolysis gasoline C
6-C
8Components selection hydrogenation, active ingredient are palladiums, and carrier is α, δ mixed phase aluminum oxide, be lamella catalyst, the palladium content that with the carrier is benchmark is the heavy % of 0.28-0.30, and reaction temperature rising is low, diolefin hydrogenation selectivity height, the ability of anti-arseniasis is stronger, but the hydrogenation activity of catalyzer is moderate.CN 1218822A discloses a kind of selective hydrogenation catalyst, form by the nickel oxide of the heavy % of 5-25, the lithium of the heavy % of 0.1-2.0 or the aluminum oxide of alkaline-earth metal and surplus, this catalyzer is that Ni is made on the alumina supporter that contains lithium or alkaline-earth metal, be applicable to the distillate that contains diolefin, particularly the selective hydrogenation process of the full distillate oil of pyrolysis gasoline has improved hydrogenation activity and stability.
Yet, for a kind of good selective hydrogenation catalyst, should have higher activity, stability and selectivity simultaneously, also unresolved this problem in the prior art.
3. summary of the invention
The invention provides a kind of selective hydrogenation catalyst with excellent activity, selectivity and stability.
Catalyzer of the present invention is by palladium metal, alkaline earth metal oxide and carrier A l
2O
3Form, wherein carrier specific surface 50-150m
2/ g is preferably 100-130m
2/ g, specific pore volume 0.35-0.55ml/g is preferably 0.40-0.50ml/g, and the hole of 5.0-10.0nm accounts for more than 70% of total pore volume, and carrier can be bar shaped, sphere or compressing tablet shape etc.
In the catalyzer be the heavy % of content 0.15-0.5 of benchmark palladium with the carrier, the heavy % of alkaline earth metal oxide content 0.1-3.0,0.1-1.0% preferably, alkaline earth metal oxide is preferably magnesium oxide.
In catalyzer set-up procedure of the present invention, at first prepare alumina supporter.Carrier by pseudo-boehmite powder and binding agent, pore-forming material etc. after kneading, moulding, 100-120 ℃ dry 2-5 hour, again at 900-1050 ℃, preferably 950-1000 ℃ following roasting 1-8 hour, preferably 2-4 hour.
The pseudo-boehmite powder is made of usual method when moulding, and used binding agent and pore-forming material also can utilize known material, and pore-forming material is the 1-4% of vehicle weight, and binding agent is the 1-2% of vehicle weight.
Alkaline earth metal oxide and palladium are to adopt to divide the mode of soaking, and at first use alkaline earth metal compounds solution incipient impregnation carrier, and the concentration of solution can be determined by the cubage of alkaline earth metal oxide on the predetermined last catalyzer.Behind the dipping, after 100-120 ℃ of dry 1-3 hour, again at 300-600 ℃, preferably 400-500 ℃ following roasting 1-6 hour, preferably 2-3 hour.Make the alumina supporter of the heavy % of alkaline including earth metal oxide compound 0.1-3.0 like this.
Above-mentioned alkaline earth metal compounds is the compound of magnesium, preferred magnesium nitrate.
Get the carrier of a certain amount of alkaline including earth metal oxide compound, preimpregnation in distilled water, drain after, again with the compound solution of palladium dipping, the concentration of solution can be determined by the cubage of palladium on the predetermined last catalyzer.Palladium compound can be a kind of in the known palladium compound, the preferably chlorate of palladium, nitrate, and it is acid that solution preferably is, and PH=1.5-2.5 regulates with hydrochloric acid.The dipping back is after 100-120 ℃ of dry 1-3 hour, again at 300-600 ℃ of following roasting 1-6 hour.
Catalyzer of the present invention is a precious metals palladium catalyst, because of alumina carrier surface through the alkaline earth metal oxide modification, reduced the acidity of carrier surface, improved activity of such catalysts to a certain extent, reduced the growing amount of polymkeric substance, the stability of catalyzer is improved, has prolonged the regeneration period of catalyzer; Find by repetition test simultaneously, by the specific surface 50-150m that selects the suitable carriers raw material and under suitable operational condition, make
2/ g, specific pore volume 0.35-0.55ml/g, the hole of 5.0-10.0nm accounts for the alumina supporter more than 70% of total pore volume, is applied to make in the selective hydrogenation catalyst that catalyst hydrogenation activity and selectivity all increase significantly.
4. embodiment
Example 1 (according to the present invention)
(1). carrier preparation
After getting 1000 gram pseudo-boehmites, 40 gram sesbania powder and being mixed, adds 500 milliliters and contain the aqueous solution that citric acid 20 restrains, after 4 hours, 960 ℃ of following roastings 3 hours, the strip carrier that makes had following physical properties again through kneading, extrusion moulding, 110 ℃ of dryings:
Specific surface 118m
2/ g, specific pore volume 0.42ml/g.
The hole of pore radius 5.0-10.0nm accounts for 75% of total pore volume.
(2). Preparation of catalysts
A. take by weighing 2.04 and restrain the Palladous chloride powder that the palladium content are no less than 59 heavy %, be dissolved in 315 ml distilled waters, add appropriate hydrochloric acid, regulate PH=1.5-2.5, make palladium chloride solution.
B. weighing magnesium nitrate crystal 16 grams are dissolved in the distilled water, make 210 milliliters of magnesium nitrate solutions.
C gets carrier 500 grams that step (1) makes, and above-mentioned magnesium nitrate solution is sprayed on it, then after under 120 ℃ dry 2 hours, again 450 ℃ of following roastings 3 hours.
D places distilled water with above-mentioned magnesium-containing carrier, after 30 minutes, drains carrier, is dipped in the above-mentioned palladium chloride solution.After 60 minutes, surplus liquid substantially transparent is analyzed palladium content wherein, and not enough 20ppm illustrates that palladium almost completely is adsorbed onto on the carrier.After taking-up drains, dry, roasting and soak magnesium after identical.
So just made catalyst A, the content of its palladium on carrier is 0.24 heavy %, and the content of MgO is 0.5 heavy %.
Example 2 (comparative sample)
(1). carrier preparation
The batching of carrier is identical with example 1 with extrusion moulding, and just the maturing temperature of carrier is 1100 ℃, and 3 hours time, the strip carrier that makes has following physical properties:
Specific surface 38m
2/ g, specific pore volume 0.26ml/g.
The hole of pore radius 5.0-10.0nm accounts for 36% of total pore volume.
(2). Preparation of catalysts is with example 1
So just made catalyst B, the content of its palladium on carrier is 0.24 heavy %, and the content of MgO is 0.5 heavy %.
Example 3 (comparative sample)
(1). the preparation of carrier
Method preparation by example 1.
(2). Preparation of catalysts
A takes by weighing the Palladous chloride powder that 2.04 gram palladium content are no less than 59 heavy %, is dissolved in 315 ml distilled waters, adds appropriate hydrochloric acid, regulates PH=1.5-2.5, makes palladium chloride solution.
B gets carrier 500 grams that step (1) makes and places distilled water, after 30 minutes, drains carrier, is dipped in the above-mentioned palladium chloride solution.After 60 minutes, surplus liquid substantially transparent is analyzed palladium content wherein, and not enough 20ppm illustrates that palladium almost completely is adsorbed onto on the carrier.After taking-up drains, after under 120 ℃ dry 2 hours, again 450 ℃ of following roastings 3 hours.
So just made catalyzer C, the content of its palladium on carrier is 0.24 heavy %.
Example 4 (according to the present invention)
Carrier and Preparation of catalysts just take by weighing the Palladous chloride powder that 1.70g palladium content is no less than 59 heavy % with example 1, are dissolved in 315 ml distilled waters, add appropriate hydrochloric acid, regulate PH=1.5-2.5, make palladium chloride solution.The content of palladium on carrier is 0.20 heavy %, and the content of MgO is 0.5 heavy %, makes catalyzer D.
Example 5 (according to the present invention)
Carrier and Preparation of catalysts are with example 1, and just weighing magnesium nitrate crystal 32 grams are dissolved in the distilled water, make 210 milliliters of magnesium nitrate solutions.The content of palladium on carrier is 0.24 heavy %, and the content of MgO is 1.0 heavy %, makes catalyzer E.
Example 6
This example is catalyzer of the present invention and comparative catalyst's active appraisal experiment.
With example 1,2,3,4,5 catalyst A that make, B, C, D, E adopts the continuous evaluating apparatus of pressurization, simulation industrial operation condition, activity, the selectivity of investigation original catalyst particle size.Reaction tubes is Φ 27 * 3mm stainless steel tube, and the outer chuck of adorning of pipe feeds the hot water heating, and tube hub is adorned the Thermal couple casing pipe of a Φ 4 * 1mm.Beds is filled with the glass sphere of Φ 3mm up and down.
Test is taken from Qilu Petrochemical company olefin plant cracker with pyrolysis gasoline, diene value 13.68gI/100g, and iodine number 41.40gI/100g, 74 ℃ of initial boiling points are done 150 ℃.Hydrogen purity is for working energetically 99.99% (volume).At first catalyzer is reduced, by hydrogen gas space velocity 120h
-1Amount feed hydrogen, at 90 ℃ of following reductase 12s hour.Feed pyrolysis gasoline then and hydrogen reacts, condition is: pyrolysis gasoline volume space velocity 6h
-1, 60 ℃ of temperature of reaction, hydrogen to oil volume ratio 20, pressure 2.7MPa, 20 hours time.Test-results sees Table 1.
Table 1
| Project | A | B | C | D | E |
| Product diene value, gI/100g oil | 0.76 | 1.18 | 0.99 | 0.83 | 0.68 |
| The product iodine number, gI/100g oil | 31.90 | 32.21 | 30.81 | 32.57 | 32.53 |
| The diolefin hydrogenation rate, % | 94.44 | 91.37 | 92.76 | 93.93 | 95.03 |
| The diolefin hydrogenation selectivity, % | 80.95 | 76.55 | 74.96 | 83.21 | 84.58 |
Table 1 shows, does not add the C of alkaline-earth metal, its diolefin hydrogenation rate and diolefin hydrogenation selectivity and catalyst A of the present invention, and D, E compares, and certain gap is arranged.
Do not adopt the B of carrier of the present invention, its diolefin hydrogenation rate and diolefin hydrogenation selectivity and catalyst A of the present invention, D, E compares, and is far apart.
Example 7
This example is catalyst A of the present invention and industrial catalyst F (external product, Pd/Al
2O
3System, the heavy % of Pd content 0.3) activity stability comparative evaluation experiment.Testing apparatus, raw material and appreciation condition are with example 6.Test-results sees Table 2.
Table 2
| The runtime/sky | A | F | ||
| Product diene value, gI/100g oil | The diolefin hydrogenation rate, % | Product diene value, gI/100g oil | The diolefin hydrogenation rate, % | |
| 5 | 0.79 | 94.23 | 0.89 | 93.49 |
| 10 | 0.83 | 93.93 | 0.94 | 93.13 |
| 15 | 0.92 | 93.27 | 1.03 | 92.47 |
| 20 | 0.99 | 92.76 | 1.15 | 91.59 |
| 25 | 1.02 | 92.54 | 1.27 | 90.72 |
By table 2 as seen, no matter catalyzer of the present invention is activity or activity stability, all is better than comparative catalyst F.
Claims (7)
1. a selective hydrogenation catalyst is characterized in that this catalyzer is by palladium metal, alkaline earth metal oxide and carrier A l
2O
3Forming, is that norm metal palladium content is the heavy % of 0.15-0.5 with the carrier, and alkaline earth metal oxide content is heavy %, wherein carrier specific surface area 50-150m of 0.1-3.0
2/ g, specific pore volume 0.35-0.55ml/g, the hole of 5.0-10.0nm accounts for more than 70% of total pore volume.
2. according to the described catalyzer of claim 1, it is characterized in that described carrier specific surface area 100-130m
2/ g, specific pore volume 0.40-0.50ml/g.
3. according to the described catalyzer of claim 1, it is characterized in that described alkaline earth metal oxide content take in the carrier as the heavy % of benchmark 0.1-1.0.
4. according to the described catalyzer of claim 1, it is characterized in that described alkaline earth metal oxide is a magnesium oxide.
5. according to the described catalyzer of the arbitrary claim of claim 1 to 4, it is characterized in that described alumina supporter be by pseudo-boehmite and binding agent, pore-forming material after kneading, moulding, 100-120 ℃ drying, make 900-1050 ℃ of following roasting again.
6. according to the described catalyzer of claim 5, it is characterized in that described alumina supporter maturing temperature is 950-1000 ℃.
7. the described catalyzer of the arbitrary claim of claim 1 to 4 is applicable to the one-stage selective hydrogenation of gasoline splitting process or is applicable to C
3-6The selective hydrogenation of distillate camber unsaturated hydrocarbons generates the process of monoolefine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011428384A CN1181165C (en) | 2001-12-30 | 2001-12-30 | Selective hydrogenation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011428384A CN1181165C (en) | 2001-12-30 | 2001-12-30 | Selective hydrogenation catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1429889A CN1429889A (en) | 2003-07-16 |
| CN1181165C true CN1181165C (en) | 2004-12-22 |
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1313205C (en) * | 2004-04-02 | 2007-05-02 | 中国石油天然气股份有限公司 | A selective hydrogenation, monoolefin isomerization catalyst, preparation method and application |
| CN101433845B (en) * | 2008-06-11 | 2011-09-07 | 中国石油天然气股份有限公司 | A kind of selective hydrogenation catalyst and preparation method thereof |
| JP6378902B2 (en) * | 2014-03-10 | 2018-08-22 | 日本ケッチェン株式会社 | Hydrotreating catalyst, method for producing the catalyst, and hydrotreating method for hydrocarbon oil using the catalyst |
| CN109395717B (en) * | 2017-08-18 | 2021-09-03 | 中国石油化工股份有限公司 | High-efficiency selective hydrogenation catalyst for polycyclic aromatic hydrocarbon |
-
2001
- 2001-12-30 CN CNB011428384A patent/CN1181165C/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1429889A (en) | 2003-07-16 |
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