CN1123310A - Hydrocarbon hydrodesulfurization catalyst and preparation method thereof - Google Patents
Hydrocarbon hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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- CN1123310A CN1123310A CN 94114194 CN94114194A CN1123310A CN 1123310 A CN1123310 A CN 1123310A CN 94114194 CN94114194 CN 94114194 CN 94114194 A CN94114194 A CN 94114194A CN 1123310 A CN1123310 A CN 1123310A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 title abstract 2
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011787 zinc oxide Substances 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000001246 bromo group Chemical class Br* 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite 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
- 239000011425 bamboo Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 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
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The hydrocarbon hydrodesulfurization catalyst is prepared by using gamma-alumina modified by zinc oxide as a carrier, using cobalt and molybdenum as active components and adopting cobalt and molybdenum co-immersion liquid for one-time immersion. The prepared catalyst comprises the following components: CaO 1-10% (wt), MnO 5-18% (wt), ZnO 1-15% (wt), and gamma Al in balance2O3The catalyst has the advantages of high hydrodesulfurization activity, simple preparation process, low energy consumption and good catalyst stability, and can be used for hydrodesulfurization of petroleum fractions.
Description
The present invention relates to a kind of hydrodesulfurizationof of hydrocarbons and urge, more particularly, relate to a kind of γ-Al of modified zinc oxide than agent
2O
3For wearing body, cobalt, molybdenum be the catalyzer (Co-Mo/ γ-Al of active constituent
2O
3-ZnO) preparation method.
Hydrodevulcanizing catalyst for hydro-carbons stone by with the petrochemical complex industrial production in the important process process that is absolutely necessary, strict day by day along with the processing of high-sulpur crude and environmental requirement, a kind of highly active Hydrobon catalyst of hydrodesulfurizationof of hydrocarbons arts demand.Catalyzer used on the current technology is an aluminum oxide, or with titanium oxide, is loaded with molybdenum on the modified aluminas such as silicon oxide or/and tungsten, and cobalt is or/and the catalyzer of nickel.As European patent prospectus (publication number 0 on October 29th, 1986,199,399) and the disclosed Hydrobon catalyst of Chinese patent disclosure specification sheets on March 21st, 90 (publication number CN1040610A) be with the titanium oxide modified aluminas as carrier, active ingredient is cobalt, molybdenum, nickel.On November 6th, 1985 Europe specially and the disclosed Hydrobon catalyst of prospectus (publication number 0,160,475) be with silica modified aluminum oxide as carrier, active ingredient is the cobalt molybdenum.
Traditional immersion type cobalt molybdenum/gamma-alumina catalyst generally adopts the step impregnation method preparation, and complex process is unfavorable for energy-conservation.As above-mentioned European patent 0160475 disclosed Hydrobon catalyst is exactly to carry at the sieve and silica-sesquioxide of making at first to flood molybdenum salt (molybdenum oxide content account for finished catalyst weight 15%) drying on this, after the roasting, flood cobalt salt (cobalt oxide content account for finished catalyst weight 5%) again, drying, roasting and making.
The objective of the invention is to prepare modified aluminium oxide supports by with zinc oxide aluminum oxide being carried out modification, single-steeping cobalt molybdenum co-impregnated solution is prepared the COMo/ γ Al of high hydrodesulfurization activity
2O
3-ZnO catalyst.
The scheme of the present invention's design is as follows:
The 1. preparation of carrier,
1. choosing pore volume is 0.5--1.5 milliliter/gram, (preferred 0.7--1.0 milliliter/gram), specific surface is the 100--350 meters squared per gram, the aluminum hydroxide solid elastomer of (preferred 200--300 meters squared per gram), add the proportional binding agent of aluminum hydroxide solid elastomer, (as: water and nitric acid) and expanding agent are (as polyvinyl alcohol, polyacrylamide, field mountain valley with clumps of trees and bamboo powder etc.), add zinc salt then as zinc acetate, zinc nitrate etc., said mixture is mixed alunite, extruded moulding is at last in 110--150 ℃ of oven dry 2--4 hour, in 480--600 ℃ of roasting 4--8 hour, can make and contain znO1--20% (wt), preferably γ--the Al of 1--10% (wt)
2O
3Carrier,
2. choosing specific surface is 100-300 meters squared per gram (preferred 200--300 meters squared per gram), and pore volume is 0.5--1.5ml/g (preferred 0.7--1.0ml/g), and the most probable radius is γ-Al of 2.0--20.0nm (preferred 2.0--10.0nm)
2O
3, with the zinc solution of its pore volume equivalent, as zinc acetate, zinc nitrate dipping γ Al
2O
31--4 hour, in 110--150 ℃ of oven dry 2--6 hour,, can make and contain the preferably γ Al of 1--10% (Wt) of ZnO 1--20% (wt) then in 500--600 ℃ of roasting 4--8 hour
2O
3Carrier.
Measure specific surface, pore volume, pore radius with pressing the record method.
2. Preparation of catalysts.
Getting a certain amount of concentration is 15--28%, the 22--28% ammoniacal liquor that is preferably, the cobalt salt that adds aequum, as Xiao Suangu and Cobaltous diacetate, under constantly stirring, add a certain amount of quadrol, make it to form stable cobalt, quadrol complex compound, the amount that makes quadrol is the 1/50--1/7 of Xiao Suangu weight, be preferably 1/20--1/15, add the ammonium molybdate of aequum then, be stirred to dissolving fully.
Get a certain amount of above-mentioned co-impregnated solution, impregnated carrier 1--10 hour, preferably 2--4 hour, in 110--150 ℃ of oven dry 2--6 hour.In 480--600 ℃ of roasting 3--8 hour, in the catalyzer of the present invention preparation, cobalt oxide and molybdenum oxide content are respectively 1--10% (wt), preferably 1--5% (wt) and 5--18% (wt) 8--14% (wt) preferably, ZnO content is 1--15%, and all the other are γ--Al
2O
3
The present invention is because carrier adopts γ--the Al of ZnO modification
2O
3Thereby, improved the desulphurizing activated of catalyzer, and owing to adopted single-steeping Co--Mo co-impregnated solution.Save operation steps, reduced energy consumption.This catalyzer can be used in the secondary hydrogenation sulfur removal technology of petroleum naphtha, reformer feed gasoline, kerosene, catalytic diesel oil, coker gas oil, pyrolysis gasoline.
Following example is further illustrated technical characterictic of the present invention:
Example 1
4.3 gram (65%) nitric acid and 5.8 gram zinc nitrates are dissolved in 100 milliliters the ionized water, after stirring, adding 100 gram pore volumes is 0.88 milliliter/gram, specific surface is in the aluminum hydroxide solid elastomer powder of 295 meters squared per gram, be mixed, add the blue or green powder in 5 gram fields again, mix behind the mixing and pinch 3 times, be extruded into φ 1.5mm bar, in 120 ℃ of oven dry 4 hours.550 ℃ of roastings 4 hours.Make ZnO--γ Al
2O
3Carrier (A), its character see Table 1. examples 2.
Choose 0.49 milliliter of pore volume/gram, specific surface 244 meters squared per gram, intensity 162N/cm, most probable radius are γ-Al of 4.0nm
2O
3(φ 1.5mm strip) 100 grams flooded 2 hours with 80 milliliters of aqueous solution that contain zinc nitrate 7.5 grams.In 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 4 hours made ZnO--γ Al
2O
3Carrier (B).
Example 3.
The preparing carriers method is with example 1, but the add-on of nitric acid and zinc nitrate is respectively 5.0 grams and 48.5 grams.Make ZnO--γ Al
2O
3Carrier (C)
Table 1.
| Bearer number | ZnO content | Pore volume (ml/g) | Specific surface m 2/g | Intensity (N/cm) | Most probable radius (nm) |
| ????A ????B ????C | ????2.0 ????2.0 ????15.0 | ?0.59 ?0.48 ?0.52 | ?307 ?229 ?264 | ?153 ?140 ?137 | ????3.9 ????4.2 ????5.6 |
Example 4.
Preparation of Catalyst:
21.5 gram Xiao Suangus are joined in the ammoniacal liquor of 90 milliliters of 25--28%, stir, add 1.0 milliliters of quadrols, add 24.7 gram ammonium molybdates then, constantly be stirred to and form red sauce solution.Carrier in the 100 gram examples 1, was dried 4 hours in 120 ℃ after 2 hours with this steeping fluid dipping.In 500 ℃ of roastings 4 hours, just make Co-Mo γ-Al of the present invention
2O
3-ZnO catalyst (A-1), wherein molybdenum oxide (MoO
3) content is 13.27% (wt), cobalt oxide (CoO) content is 3.79% (wt), and zinc oxide (ZnO) content is 2.0% (wt), and physical parameter is: the specific surface of this catalyzer is 225.7m
2/ g gram, pore volume is 0.44ml/g, the most probable radius is 6.6nm.
Example 5.
The preparation method is with example 4, but the add-on of Xiao Suangu and ammonium molybdate is respectively 14.2 grams and 15.2 grams, the CoMo/ γ-Al that makes
2O
3-znO catalyzer (A-2), its MoO
3Content is 8.2% (wt), and CoO content is 2.5% (wt), and ZnO content 2.0%, its specific surface are 232.3m
2/ g, pore volume are 0.46ml/g.
Example 6.
Catalyst desulfurizing activity and simultaneous test.
Get 1.0 milliliters of catalyzer (A-1) in the example 4, granularity is the 20--40 order, vulcanizes in pressurized reactor.Cure conditions is: 300 ℃ of temperature, oxygen partial pressure 3.0MPa, air speed 4.0h (volume), H
2/ oil=500: 1 (volume), vulcanized oil is for containing CS
2The hexanaphthene of 6% (wt), curing time 3 hours.
The sulfuration back feeds the hexanaphthene that contains thiophene, and its sulphur content is 1000ppm, in 300 ℃ of temperature, and hydrogen partial pressure 3.0MPa, air speed is 4.0h (volume), H
2: oil=condition under react at 500: 1, it gives birth to olefiant sulphur content is 4.3PPm.
The contrast experiment: many at home cover reformer feeds of getting Wenzhou catalyst plant production give the reformer feed that uses in the hydrodesulfurization unit and give Hydrobon catalyst 481-3, under above-mentioned similarity condition, compare examination, it gives birth to olefiant sulphur content is 5.6PPm, finds out its desulphurizing activated 481-3 of being higher than catalyzer of catalyzer of the present invention thus.
Example 7.
Get 120 milliliters of catalyzer (A-1) in the example 4, granularity is 2--3mm, vulcanizes in small-sized hydrogenation evaluating apparatus, and cure conditions is: 290 ℃ of temperature, pressure are 4.0MPa, and air speed is 2.0h
-1, H
2/ oil=400: 1, vulcanized oil is for containing 1%CS
2Virgin kerosene, curing time is 10 hours, sulfuration back feeds pyrolysis gasoline, its sulphur content is 504PPm, the bromine valency is 24.6 gram bromines/100 gram oil, in 310 ℃, hydrogen partial pressure 2.9MPa, air speed is 2.0h, H
2React under the condition of/oil ratio=4: 1 (molecular ratio), activity test the results are shown in Table 2.
To producing through the 1. Japanese Girdler catalyst of test company, the G-35B catalyzer that use in now many at home and abroad cover pyrolysis gasoline secondary hydrogenation desulfurizers are under the example 6 identical sulfuration and reaction conditions.With the sulphur content is 326.2PPm, and the bromine valency is that the pyrolysis gasoline of 24.4 gram bromines/100 gram oil is that raw material compares examination.
Simultaneous test is 2.: get Chemical Inst., Lanzhou Chemical Industry Co and produce, 120 milliliters of the 8602B catalyzer that pyrolysis gasoline secondary hydrogenation desulfurization of domestic many covers and reformer feed give hydrodesulfurization unit now have been used for, granularity 20--3mm, under the sulfuration and reaction conditions identical with example 6, with the sulphur content is 405PPm, and the bromine valency is that the pyrolysis gasoline of 25.0 gram bromines/100 gram oil is that raw material compares examination.
Table 2.
| Catalyzer | Product sulphur content (PPm) | Product bromine valency (g bromine/100g oil) | Desulfurization degree |
| ????A-1 ??G-35B ??8602G | ????0.7 ????1.2 ????1.0 | ????0.10 ????0.11 ????0.11 | ????99.9 ????99.6 ????99.7 |
Claims (6)
1. one kind with γ-Al
2O
3Be carrier, active ingredient is a cobalt, and the Hydrodevulcanizing catalyst for hydro-carbons of molybdenum is characterized in that, carrier ZnO modification, single-steeping Co-Mo co-impregnated solution, the CoMo/ γ-Al of preparation
2O
3-znO catalyzer, carrier and catalyzer prepare by following method:
The preparing carriers method:
1. with pore volume 0.5--1.5 milliliter/gram, specific surface is the aluminum hydroxide solid elastomer of 100--350 meters squared per gram, add a certain proportion of tackiness agent and expanding agent, add zinc salt then, mix together and pinch, extruded moulding is at last in 110--150 ℃ of oven dry 2--4 hour, in 480--600 ℃ of roasting 4--8 hour, make the γ that contains ZnO 1--20% (wt)--Al
2O
3Carrier.
2. be the 100--300 meters squared per gram with specific surface, pore volume is 0.5--1.5 milliliter/gram, and the most probable radius is γ-Al of 2.0--20.0 centimetre
2O
3, use and the zinc solution of its pore volume equivalent dipping 1--4 hour, in 110--150 ℃ of oven dry 2--6 hour,, make the γ-Al that contains ZnO 1-20% (wt) then in 500--600 ℃ of roasting 4--8 hour
2O
3Carrier.
Method for preparing catalyst:
With a certain amount of concentration is the ammoniacal liquor of 15--28%, adds the aequum cobalt salt, adds a certain amount of quadrol under constantly stirring, and the amount that makes quadrol is the 1/50-1/7 of cobalt salt weight, adds the ammonium molybdate of aequum then under constantly stirring; Make the Co-Mo co-impregnated solution, with a certain amount of co-impregnated solution impregnated carrier 1--10 hour, in 110--150 ℃ of oven dry 2--6 hour,, make the catalyzer that is respectively 1--10% (wt) and 5--18% (wt) with respect to the content of catalyst cobalt and molybdenum in 480--600 ℃ of roasting 3--8 hour.
2. by the described carrier of claim 1, it is characterized in that: described binding agent can be water and nitric acid; Described expanding agent can be the polyethylene enol, polyacrylamide, the blue or green powder in field; Described zinc salt can be zinc acetate or zinc nitrate.
3. by claim 1 or 2 described carriers, it is characterized in that: its pore volume of described aluminum hydroxide solid elastomer is 0.7--1.0 milliliter/gram, and specific surface is the 200--300 meters squared per gram; Described γ-Al
2O
3Its pore volume is 0.7--1.0 milliliter/gram, and specific surface is the 200--300 meters squared per gram, and the most probable radius is 2.0--10.0nm.
4. by the described carrier of claim 3, it is characterized in that being described γ-Al
2O
3Contain ZnO1--10% (weight) in the carrier
5. by the described catalyzer of claim 1, the concentration that it is characterized in that ammoniacal liquor is 22--28%; Described cobalt salt can be Xiao Suangu and Cobaltous diacetate; Quadrol/Xiao Suangu can be 1/20--1/5 (wt).
6. by claim 1 or 5 described catalyzer, it is characterized in that the carrier impregnation time is 2--4 hour, described molybdenum oxide content is 1--5% (wt), and cobalt oxide content is 8--14% (wt).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114194A CN1043359C (en) | 1994-11-25 | 1994-11-25 | Hydrocarbon hydrodesulfurization catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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