CN103627425B - Residual oil hydrodesulfurization method - Google Patents
Residual oil hydrodesulfurization method Download PDFInfo
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- CN103627425B CN103627425B CN201210302542.5A CN201210302542A CN103627425B CN 103627425 B CN103627425 B CN 103627425B CN 201210302542 A CN201210302542 A CN 201210302542A CN 103627425 B CN103627425 B CN 103627425B
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 18
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 13
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 13
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 150000001868 cobalt Chemical class 0.000 claims abstract 5
- 239000000454 talc Substances 0.000 claims abstract 4
- 229910052623 talc Inorganic materials 0.000 claims abstract 4
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- 239000012530 fluid Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- -1 metal oxide compound Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 3
- 239000011780 sodium chloride Substances 0.000 claims 3
- 235000012222 talc Nutrition 0.000 claims 3
- 238000001035 drying Methods 0.000 abstract description 9
- 159000000000 sodium salts Chemical class 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000004480 active ingredient Substances 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000005864 Sulphur Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000011068 loading method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000003252 repetitive effect Effects 0.000 description 6
- 238000005201 scrubbing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- LCSNMIIKJKUSFF-UHFFFAOYSA-N [Ni].[Mo].[W] Chemical compound [Ni].[Mo].[W] LCSNMIIKJKUSFF-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a residual oil hydrodesulfurization method; the catalyst is prepared by dripping ammonia water to prepare terephthalic acid solution, and adding nickel salt or cobalt salt, urea and ammonium salt to obtain impregnation liquid with a molar ratio of 2:1:2.5-5: 1-5; soaking the soaking solution on the surface of the carrier in the same volume, standing at room temperature, crystallizing, washing, and drying at 80-120 ℃ to obtain nickel salt or cobalt salt hydrotalcite; preparing a sodium salt solution of VIII-group acid, wherein the concentration is 14mol/L, then immersing nickel salt or cobalt salt talc into the sodium salt solution of VIII-group acid, adjusting the pH value to 4.5, washing the obtained solid particles, drying at 80-100 ℃, and roasting at 300-700 ℃ to obtain the catalyst.
Description
Technical field
The present invention relates to a kind of method of residuum hydrodesulfurization, is catalysis process for hydrogenating residual oil in fixed bed residual hydrogenation equipment.
Background technology
Along with crude oil heaviness, in poor quality aggravation in world wide, the increasingly stringent of environmental regulation, the demand of market to light-end products but increases year by year simultaneously, and the deep processing of development residual oil is petroleum refining industry's task of top priority.Hydrogen addition technology is faced with great challenge as main processing means, in the urgent need to developing better hydrogenation technique and more highly active hydrogenation catalyst.Common residuum hydrodesulfurization catalyzer take aluminum oxide as carrier matrix, with Mo/W and Ni/Co for active ingredient, appropriate auxiliary agent can certainly be added according to different requirements, as Si, Ti, Zr, B and P etc., and the current industrial main employing pickling process of preparation method.Describing with activated carbon in CN102049252A is the method that carrier loaded active metal Mo, Ni prepare catalyst for hydrotreatment of residual oil, but in conjunction with insecure between active ingredient and carrier, the phenomenon that catalytic performance also may cause loss of active component thus can not be given full play to; Reporting in CN1162621 with aluminum oxide is the method that carrier to load metal Mo, Ni prepare catalyst for hydrotreatment of residual oil, but due to support preparation method and active constituent loading method, active ingredient degree of scatter is inadequate, and activity is lower.
Adopting in the process of preparation catalyst has two factors directly to affect the dispersity of active metal on carrier.First by the surface tension of immersion solvent and the impact of solvation, be often that active ingredient to be assembled at carrier surface and formed large particle crystal at steeping process; Secondly, because active ingredient still forms extensive chemical effect with surface in steeping process, be combined more firmly with carrier to make active ingredient, often need to carry out roasting to it after catalyzer drying He before roasting, Metallic Solids in the process condenses and gradually grows up as oarse-grained crystallization.The metal specific surface area of the load type metal catalyst so obtained is little, and metal dispersity only can reach about 35%, limits the further raising of the catalytic capability of loaded catalyst.
Hydrotalcite (LayeredDoubleHydroxide is called for short LDH) has similar structure to the magnesium hydroxide of laminated structure, is the product that two valency magnesium ions in the little octahedron of laminate are replaced by the ionic metal moiety of trivalent.In LDH, two-dimentional laminate longitudinal arrangement forms three-dimensional crystalline structure, and the atom on laminate, with covalent bonds, is weak chemical bond between interlayer anion and laminate, as ionic linkage, hydrogen bond etc.LDH laminate being introduced Tricationic makes laminate skeleton positively charged, and the negatively charged ion of interlayer opposite charges balances each other with it, makes whole crystal show electric neutrality.The principle of hydrotalcite can be formed according to suitable divalent-metal ion and trivalent metal ion, the atom of metal active constituent coordinates with other divalent metal atom and introduces hydrotalcite laminate by someone, the joint effect of the orientation effect of and crystal Atom minimum by lattice energy, the main part of this metal active, in the dispersion of hydrotalcite precursor camber, can prepare the metal load type catalyst of excellent property.
In CN1483512A, describe to contain the process that palladium LDHs is precursor power metal catalyst, and the application in residual oil model compound anthraquinone and derivative hydrogenation given by this catalyzer.But because metallic palladium belongs to precious metal, cost is higher, is difficult to industrial applications.Therefore the catalyzer of the common metal such as preparation load molybdenum tungsten nickel is only had just to have the value of industrial application.
Summary of the invention
The object of this invention is to provide a kind of method of residuum hydrodesulfurization.The method for preparing catalyst of the method overcomes the defect of conventional pickling process, active metal can be made to be highly dispersed in carrier bore surface by this method, thus the activity of catalyzer is increased substantially.
The catalyzer that the method for residuum hydrodesulfurization of the present invention is used adopts in-situ deposition technology fabricated in situ in carrier surface hole to contain the hydrotalcite composite material of group VIII metal, adopt ion exchange method that the anion metathesis containing group vib metal is entered hydrotalcite on this basis, formed with polyanionic post support matrix material, then through roasting obtain many metals carrier surface and duct inner height dispersion catalyzer.Wherein group VIII metal is Ni or Co, the 1wt%-9wt% that content (in metal oxide weight) is catalyst weight, and group vib metal is Mo or W, the 5wt%-15wt% that content (in metal oxide weight) is catalyst weight.The pore volume of catalyzer is: 0.5-1.0ml/g, and specific surface area is 190-280m
2/ g.
The concrete preparation method of this catalyzer is as follows:
A. the preparation of steeping fluid: first prepare terephthalic acid solution, drips ammoniacal liquor and makes it just dissolve in the process of preparation; Then add nickel salt (or cobalt salt), urea and ammonium salt and obtain steeping fluid, in steeping fluid, the mol ratio of terephthalic acid, nickel salt (or cobalt salt), urea and ammonium salt is 2:1:2.5-5:1-5.Divalent nickel salt used can be Ni (NO
3)
2, NiCl
2, Ni (AC)
2, NiBr
2in any one.
B. the preparation of nickel salt (or cobalt salt) hydrotalcite.Adopt equi-volume impregnating to be impregnated into carrier surface steeping fluid, then room temperature leaves standstill 6-24h, then moves to crystallization 24-32h in Pressure vessel, and after crystallization, for several times, dry 12-24h at 80 DEG C-120 DEG C, obtains nickel salt (or cobalt salt) hydrotalcite in washing.Carrier used is Al
2o
3, SiO
2or any one in activated carbon, the shape of carrier is that spherical, bar shaped, Herba Galii Bungei type or cylindrical particle, granularity are between 5-200 order.Wherein Al
2o
3the crystal formation of carrier is any one in γ, η, δ, θ, α or their two or more mixing crystal formation; SiO
2mesopore or gross porosity with the pore structure of activity carbon carrier.
C. the preparation of catalyzer: the sodium salt solution of preparation VIII acid, concentration is 1-4mol/L, again nickel salt (or cobalt salt) hydrotalcite is immersed in the sodium salt solution of VIII acid, and with acid for adjusting pH value to 4.5, stir 1-2h, by the green solid particle washing obtained, dry 12-24h at 80-100 DEG C, last at 300-700 DEG C of roasting temperature 2-24 hour, preferably roasting 5-12 hour at 400-600 DEG C, hydrotalcite precursor is made to be converted into complex metal oxides completely, namely secure satisfactory grades loose loading type residuum hydrodesulfurization catalyzer, wherein the sodium of VIII acid is Na
2moO
42H
2o, Na
2wO
42H
2o, Na
2h
9p (Mo
2o
7)
62H
2o, Na
2h
9p (W
2o
7)
62H
2o, or the mixing of wherein two kinds of salt, the acid of adjust ph is nitric acid or hydrochloric acid.
With Al in the selection of carrier
2o
3for optimum, not only because Al
2o
3carrier has suitable pore structure and satisfactory stability, Another reason is aluminium source synthesis nickel salt (or cobalt salt) hydrotalcite precursor that can utilize carrier bore surface, make firmly to be combined between active metal with carrier in the catalyzer of final preparation, thus obtain longer stability in use and work-ing life.
Adopt temperature programming hydroxide titration (H
2-O
2-TPD) method measures active metal dispersity in catalyzer prepared by the present invention, and result is all between 48-62%.And adopt catalyzer prepared by traditional pickling process, measured by same method, the dispersity of its active metal is less than 35%.
High dispersive bimetal residuum hydrodesulfurization catalyzer the present invention prepared is examined with atmospheric resid desulphurization reaction process, in whole process hydrodesulfurization process, experimental installation keeps hydrogen dividing potential drop to remain on 10-14MPa, temperature of reaction is between 300-400 ° of C, and desulfurization degree can reach 97-100%.This result illustrates, the high dispersive residuum hydrodesulfurization catalyzer of this device invention, has better activity than the catalyzer of other identical load metal used at present.
Unusual effect of the present invention is, owing to being at carrier bore surface fabricated in situ bimetal LDH, be grown on divalent metal on the laminate of the bimetal LDH lamellar precursor of carrier bore surface and sexavalence metallate ion and become high dispersing state by the impact of lattice energy, metallic cation is all transformed into its corresponding oxide compound after baking, the metallic sulfide of high dispersing is being transformed into through pre-vulcanization process, and other divalence, trivalent light metal oxide compound does not react in pre-vulcanization process, and play separant and promotor effect at catalyst pores internal surface.By metal load type catalyst prepared by the method, stronger interaction is had between its active ingredient and carrier, enable active metal component stably be present in the bore surface of carrier, this catalyzer is used for residuum hydrodesulfurization treating processes, has stronger activity and work-ing life.
The object of the invention is to prepare a kind of novel residual oil Hydrobon catalyst, it is characterized in that catalyzer is prepared by stratiform presoma LDHs, the metal height dispersion of load, catalytic activity is higher.
Embodiment
Embodiment 1
The present embodiment is with γ-Al
2o
3as carrier, with metal oxide NiO and MoO
3residuum hydrodesulfurization catalyzer is prepared, wherein NiO content 2.5wt%, MoO as active ingredient
3content 8.5wt%.
Take 12.5g terephthalic acid and put into beaker, add 350ml deionized water, dropping ammoniacal liquor also fully stirs and makes it dissolve, and then adds 11.0gNi (NO
3)
26H
2o, 4.5g urea and 4.5g ammonium nitrate, obtain steeping fluid after dissolving.Steeping fluid is added lentamente and is equipped with 100g γ-Al
2o
3beaker in, dropping limit, limit is stirred, and dropwises rear Keep agitation 5min, and then place in room temperature and be no less than 12h, move to 120 DEG C of crystallization 24h in Pressure vessel, crystallization is complete, and for several times, dry 12h at 100 DEG C, obtains TAMA-Ni-Al-LDHs/ γ-Al in washing
2o
3.
Take 12.0g (NH
4)
6mo
7o
244H
2o, adds the abundant stirring and dissolving of 200ml water, is then added drop-wise to TAMA-Ni-Al-LDHs/ γ-Al
2o
3above and stir, drip the HNO of 4mol/L simultaneously
3solution, adjust ph to 4.5, settlement separate after stirring 100min, by the washing of green solid particle, drying, spend deionized water repetitive scrubbing, gained solid particulate is dry 12h at 80 DEG C, obtains Mo
7o
24 6--Ni-Al-LDHs/ γ-Al
2o
3.In 550 DEG C of air, calcine 4h again, obtain residuum hydrodesulfurization catalyzer.
Measuring 100ml catalyst loading enters in the small-sized evaluating apparatus of fixed bed residual hydrocracking, and carry out reaction evaluating with the long residuum that sulphur content is 4%, reaction pressure is 16MPa, and in product, sulphur content is 0.6%.
Embodiment 2
The present embodiment is with γ-Al
2o
3as carrier, with metal oxide CoO and MoO
3residuum hydrodesulfurization catalyzer is prepared, wherein CoO content 2.5wt%, MoO as active ingredient
3content 8.5wt%.
Take 12.5g terephthalic acid and put into beaker, add 350ml deionized water, dropping ammoniacal liquor also fully stirs and makes it dissolve, and then adds 11.0gCo (NO
3)
26H
2o, 4.5g urea and 4.5g ammonium nitrate, obtain steeping fluid after dissolving.Steeping fluid is added lentamente and is equipped with 100g γ-Al
2o
3beaker in, dropping limit, limit is stirred, and dropwises rear Keep agitation 5min, and then place in room temperature and be no less than 12h, move to 120 DEG C of crystallization 24h in Pressure vessel, crystallization is complete, and for several times, dry 12h at 100 DEG C, obtains TAMA-Co-Al-LDHs/ γ-Al in washing
2o
3.
Take 12.0g (NH
4)
6mo
7o
244H
2o, adds the abundant stirring and dissolving of 200ml water, is then added drop-wise to TAMA-Co-Al-LDHs/ γ-Al
2o
3above and stir, drip the HNO of 4mol/L simultaneously
3solution, adjust ph to 4.5, settlement separate after stirring 100min, by the washing of green solid particle, drying, spend deionized water repetitive scrubbing, gained solid particulate is dry 12h at 80 DEG C, obtains Mo
7o
24 6--Co-Al-LDHs/ γ-Al
2o
3.In 550 DEG C of air, calcine 4h again, obtain residuum hydrodesulfurization catalyzer.
Measuring 100ml catalyst loading enters in the small-sized evaluating apparatus of fixed bed residual hydrocracking, and carry out reaction evaluating with the long residuum that sulphur content is 4%, reaction pressure is 16MPa, and in product, sulphur content is 0.8%.
Embodiment 3
The present embodiment is with γ-Al
2o
3as carrier, with metal oxide NiO and WO
3residuum hydrodesulfurization catalyzer is prepared, wherein NiO content 2.5wt%, WO as active ingredient
3content 13.6wt%.
Take 12.5g terephthalic acid and put into beaker, add 350ml deionized water, dropping ammoniacal liquor also fully stirs and makes it dissolve, and then adds 11.0gNi (NO
3)
26H
2o, 4.5g urea and 4.5g ammonium nitrate, obtain steeping fluid after dissolving.Steeping fluid is added lentamente and is equipped with 100g γ-Al
2o
3beaker in, dropping limit, limit is stirred, and dropwises rear Keep agitation 5min, and then place in room temperature and be no less than 12h, move to 120 DEG C of crystallization 24h in Pressure vessel, crystallization is complete, and for several times, dry 12h at 100 DEG C, obtains TAMA-Ni-Al-LDHs/ γ-Al in washing
2o
3.
Take 17.2g (NH
4)
10w
12o
41, add the abundant stirring and dissolving of 200ml water, be then added drop-wise to TAMA-Ni-Al-LDHs/ γ-Al
2o
3above and stir, drip the HNO of 4mol/L simultaneously
3solution, adjust ph to 4.5, settlement separate after stirring 100min, by the washing of green solid particle, drying, spend deionized water repetitive scrubbing, gained solid particulate is dry 12h at 80 DEG C, obtains W
7o
24 6--Ni-Al-LDHs/ γ-Al
2o
3.In 550 DEG C of air, calcine 4h again, obtain residuum hydrodesulfurization catalyzer.
Measuring 100ml catalyst loading enters in the small-sized evaluating apparatus of fixed bed residual hydrocracking, and carry out reaction evaluating with the long residuum that sulphur content is 4%, reaction pressure is 16MPa, and in product, sulphur content is 0.9%.
Embodiment 4
The present embodiment is with γ-Al
2o
3as carrier, with metal oxide CoO and WO
3residuum hydrodesulfurization catalyzer is prepared, wherein CoO content 2.5wt%, WO as active ingredient
3content 13.6wt%.
Take 12.5g terephthalic acid and put into beaker, add 350ml deionized water, dropping ammoniacal liquor also fully stirs and makes it dissolve, and then adds 11.0gCo (NO
3)
26H
2o, 4.5g urea and 4.5g ammonium nitrate, obtain steeping fluid after dissolving.Steeping fluid is added lentamente and is equipped with 100g γ-Al
2o
3beaker in, dropping limit, limit is stirred, and dropwises rear Keep agitation 5min, and then place in room temperature and be no less than 12h, move to 120 DEG C of crystallization 24h in Pressure vessel, crystallization is complete, and for several times, dry 12h at 100 DEG C, obtains TAMA-Co-Al-LDHs/ γ-Al in washing
2o
3.
Take 17.2g (NH
4)
10w
12o
41, add the abundant stirring and dissolving of 200ml water, be then added drop-wise to TAMA-Co-Al-LDHs/ γ-Al
2o
3above and stir, drip the HNO of 4mol/L simultaneously
3solution, adjust ph to 4.5, settlement separate after stirring 100min, by the washing of green solid particle, drying, spend deionized water repetitive scrubbing, gained solid particulate is dry 12h at 80 DEG C, obtains W
7o
24 6--Co-Al-LDHs/ γ-Al
2o
3.In 550 DEG C of air, calcine 4h again, obtain residuum hydrodesulfurization catalyzer.
Measuring 100ml catalyst loading enters in the small-sized evaluating apparatus of fixed bed residual hydrocracking, and carry out reaction evaluating with the long residuum that sulphur content is 4%, reaction pressure is 16MPa, and in product, sulphur content is 1.2%.
Embodiment 5
The present embodiment is with γ-Al
2o
3as carrier, with metal oxide NiO and MoO
3residuum hydrodesulfurization catalyzer is prepared, with P as active ingredient
2o
5as promotor, wherein NiO content 2.5wt%, MoO
3content 8.5wt%, P
2o
5for 0.35wt%.
Take 12.5g terephthalic acid and put into beaker, add 350ml deionized water, dropping ammoniacal liquor also fully stirs and makes it dissolve, and then adds 11.0gNi (NO
3)
26H
2o, 4.5g urea and 4.5g ammonium nitrate, obtain steeping fluid after dissolving.Steeping fluid is added lentamente and is equipped with 100g γ-Al
2o
3beaker in, dropping limit, limit is stirred, and dropwises rear Keep agitation 5min, and then place in room temperature and be no less than 12h, move to 120 DEG C of crystallization 24h in Pressure vessel, crystallization is complete, and for several times, dry 12h at 100 DEG C, obtains TAMA-Ni-Al-LDHs/ γ-Al in washing
2o
3.
Take 10.6g (NH
4)
3[PMo
12o
40] 6H
2o, adds the abundant stirring and dissolving of 200ml water, is then added drop-wise to TAMA-Ni-Al-LDHs/ γ-Al
2o
3above and stir, drip the HNO of 4mol/L simultaneously
3solution, adjust ph to 4.5, settlement separate after stirring 100min, by the washing of green solid particle, drying, spend deionized water repetitive scrubbing, gained solid particulate is dry 12h at 80 DEG C, obtains PMo
12o
40 3--Ni-Al-LDHs/ γ-Al
2o
3.In 550 DEG C of air, calcine 4h again, obtain residuum hydrodesulfurization catalyzer.
Measuring 100ml catalyst loading enters in the small-sized evaluating apparatus of fixed bed residual hydrocracking, and carry out reaction evaluating with the long residuum that sulphur content is 4%, reaction pressure is 16MPa, and in product, sulphur content is 0.55%.
Embodiment 6
The present embodiment is with γ-Al
2o
3as carrier, with metal oxide NiO and WO
3residuum hydrodesulfurization catalyzer is prepared, with P as active ingredient
2o
5as promotor, wherein NiO content 2.5wt%, WO
3content 13.6wt%, P
2o
5for 0.35wt%.
Take 12.5g terephthalic acid and put into beaker, add 350ml deionized water, dropping ammoniacal liquor also fully stirs and makes it dissolve, and then adds 11.0gNi (NO
3)
26H
2o, 4.5g urea and 4.5g ammonium nitrate, obtain steeping fluid after dissolving.Steeping fluid is added lentamente and is equipped with 100g γ-Al
2o
3beaker in, dropping limit, limit is stirred, and dropwises rear Keep agitation 5min, and then place in room temperature and be no less than 12h, move to 120 DEG C of crystallization 24h in Pressure vessel, crystallization is complete, and for several times, dry 12h at 100 DEG C, obtains TAMA-Ni-Al-LDHs/ γ-Al in washing
2o
3.
Take 16.8g (NH
4)
3[PW
12o
40] 3H
2o, adds the abundant stirring and dissolving of 200ml water, is then added drop-wise to TAMA-Ni-Al-LDHs/ γ-Al
2o
3above and stir, drip the HNO of 4mol/L simultaneously
3solution, adjust ph to 4.5, settlement separate after stirring 100min, by the washing of green solid particle, drying, spend deionized water repetitive scrubbing, gained solid particulate is dry 12h at 80 DEG C, obtains PW
12o
40 3--Ni-Al-LDHs/ γ-Al
2o
3.In 550 DEG C of air, calcine 4h again, obtain residuum hydrodesulfurization catalyzer.
Measuring 100ml catalyst loading enters in the small-sized evaluating apparatus of fixed bed residual hydrocracking, and carry out reaction evaluating with the long residuum that sulphur content is 4%, reaction pressure is 16MPa, and in product, sulphur content is 0.58%.
Claims (5)
1. a method for residuum hydrodesulfurization, is characterized in that:
The method utilizes fixed bed residual hydrocracking device to carry out residuum hydrodesulfurization, and hydrogen divides and is pressed in 10-14MPa, and temperature of reaction is between 300-400 DEG C;
The carrier of catalyzer is Al
2o
3;
Activity component metal oxide compound is NiO or CoO, is the 1-9wt% of catalyst weight, active metal oxide MoO
3or/and WO
3for the 5-15wt% that catalyzer is heavy;
Catalyzer is prepared by following steps:
A. the preparation of steeping fluid: first prepare terephthalic acid solution, drips ammoniacal liquor and makes it just dissolve in the process of preparation; Then add nickel salt or cobalt salt, urea and ammonium salt obtain steeping fluid, the mol ratio of terephthalic acid, nickel salt or cobalt salt in steeping fluid, urea and ammonium salt is 2:1:2.5-5:1-5;
B. the preparation of nickel salt or cobalt saline talcum: adopt equi-volume impregnating to be impregnated into carrier surface steeping fluid, then room temperature leaves standstill 6-24h, then moves to crystallization 24-32h in Pressure vessel, and after crystallization, washing for several times, dry 12-24h at 80 DEG C-120 DEG C, obtains nickel salt or cobalt saline talcum;
C. the preparation of catalyzer: the ammonium salt solution of preparation group vib metal, concentration is 1-4mol/L, again nickel salt or cobalt saline talcum are immersed in the ammonium salt solution of group vib metal, and with acid for adjusting pH value to 4.5, stir 1-2h, by the green solid particle washing obtained, dry 12-24h at 80-100 DEG C, last at 300-700 DEG C of roasting temperature 2-24 hour, make hydrotalcite precursor be converted into complex metal oxides completely, obtain residuum hydrodesulfurization catalyzer;
The ammonium salt of described group vib metal is (NH
4)
6mo
7o
244H
2o, (NH
4)
10w
12o
41, (NH
4)
3[P (Mo
12o
40] 6H
2o, (NH
4)
3[PW
12o
40] 3H
2one in O; The acid of adjust ph is nitric acid or hydrochloric acid.
2. the method for residuum hydrodesulfurization according to claim 1, is characterized in that:
In steps A, divalent nickel salt used is Ni (NO
3)
2, NiCl
2, Ni (AC)
2, NiBr
2in any one.
3. the method for residuum hydrodesulfurization according to claim 1, is characterized in that:
In step B, the shape of carrier is spherical, bar shaped, Herba Galii Bungei type or cylindrical particle; Granularity is between 5-200 order.
4. the method for residuum hydrodesulfurization according to claim 1, is characterized in that: described Al
2o
3the crystal formation of carrier is any one in γ, η, δ, θ, α or their two or more mixing crystal formation.
5. the method for residuum hydrodesulfurization according to claim 1, is characterized in that:
In step C, catalyzer maturing temperature is 300-500 DEG C, and roasting time is 5-12 hour.
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| CN105176625A (en) * | 2015-07-29 | 2015-12-23 | 中南大学 | Method for desulphurization of high-sulfur coal |
| CN106607038B (en) * | 2015-10-23 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of presulfurization Hydrobon catalyst and preparation method thereof |
| RU2694370C2 (en) * | 2017-12-06 | 2019-07-12 | федеральное государственное бюджетное образовательное учреждение высшего образования "Самарский государственный технический университет" | Catalyst for deep hydrotreating of vacuum gas oil and method of its preparation |
| CN110465304A (en) * | 2019-08-28 | 2019-11-19 | 辽宁科技大学 | A kind of preparation method of high activity hydrogenation and desulphurization catalyst |
| CN116408097B (en) * | 2021-12-31 | 2024-07-30 | 中国石油天然气股份有限公司 | Cobalt-molybdenum co-impregnation solution and its preparation method and application |
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| CN1552794A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Dipping solution and preparing method thereof |
| US7538066B2 (en) * | 2005-09-29 | 2009-05-26 | Exxonmobil Research And Engineering Company | Method of preparing a hydrotreating catalyst on a support containing a rare earth metal |
| CN101663090A (en) * | 2007-03-01 | 2010-03-03 | 牛津催化剂有限公司 | Promoted carbide-based fischer-tropsch catalyst, method for its preparation and uses thereof |
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| CN1552794A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Dipping solution and preparing method thereof |
| US7538066B2 (en) * | 2005-09-29 | 2009-05-26 | Exxonmobil Research And Engineering Company | Method of preparing a hydrotreating catalyst on a support containing a rare earth metal |
| CN101663090A (en) * | 2007-03-01 | 2010-03-03 | 牛津催化剂有限公司 | Promoted carbide-based fischer-tropsch catalyst, method for its preparation and uses thereof |
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