CN115957770A - Preparation method of boiling bed residual oil hydrogenation catalyst - Google Patents
Preparation method of boiling bed residual oil hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 238000009835 boiling Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000003921 oil Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000011343 solid material Substances 0.000 claims abstract description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- -1 silicate ester Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
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- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract description 3
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- 239000012298 atmosphere Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
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- 230000023556 desulfurization Effects 0.000 description 4
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- 238000005299 abrasion Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a preparation method of a boiling bed residual oil hydrogenation catalyst, which comprises the following steps: (1) Roasting the boiling bed residual oil hydrogenation catalyst which is partially deactivated or completely deactivated to obtain a roasted material; (2) Performing demetalization treatment on the material roasted in the step (1), performing solid-liquid separation on the treated material, and drying the solid material to obtain demetalization material and filtrate; (3) Soaking the demetallized material in the step (2) with a silicon-containing solution, drying and roasting the soaked material to obtain a strengthened material, and (4) standing and filtering the filtrate obtained in the step (2) at a low temperature, and concentrating the filtered filtrate to obtain a solution; (5) And (4) impregnating the reinforced material with the solution in the step (4), drying and roasting to obtain the catalyst. The method takes the deactivated fluidized bed hydrogenation catalyst as a raw material, and the prepared catalyst has better wear resistance and catalytic activity through demetalization and strengthening treatment.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a boiling bed residual oil hydrogenation catalyst.
Background
With the increasing heavy and inferior crude oil, oil refining enterprises face a great deal of heavy and residual oil processing and utilization problems. Residua is the heaviest, most structurally complex portion of petroleum fractions that are enriched in most of the impurities in the crude oil, such as sulfur, nitrogen, heterocyclic compounds, soluble metal compounds, gums, asphaltenes, and the like, and thus are the most difficult fractions to process. The existing heavy oil hydrogenation technology is divided into four types, namely fixed bed hydrogenation treatment, fluidized bed hydrocracking, suspended bed hydrocracking and moving bed hydrogenation treatment technology. Wherein the fixed bed hydrotreatment technology is relatively mature and most widely applied. However, when the heavy residual oil raw material contains many mechanical impurities and high content of metal impurities, the bed pressure drop is easy to cause, the catalyst is quickly deactivated, and the service life is short. The boiling bed process is a good poor heavy oil and residual oil hydrotreating process because of no pressure drop, long production period, easy control of reaction temperature and adjustable raw materials. The catalyst is always in a boiling back-mixing state in the boiling bed reactor, so that the catalyst has higher requirements on the strength and the abrasion performance of the hydrogenation catalyst.
CN104549528A discloses a preparation method of an ebullated bed catalyst. The method comprises the following steps: (1) Adding reaction liquid into the bottom of the impinging stream reactor, heating, and starting a bottom stirring paddle; (2) Mixing an aqueous alkali metal aluminate solution with CO 2 Injecting gas flow into the reactor via accelerating tube, atomizing the alkali metal aluminate solution, and mixing with CO 2 Carrying out gas-liquid impinging stream reaction on the gas flow to generate aluminum hydroxide crystal nuclei, and entering a settling zone; (3) After the gas-liquid impinging stream is finished, continuously adding an acidic aluminum salt aqueous solution and an alkali metal aluminate aqueous solution or an alkaline precipitator into the feed inlets II and III at the same time, adjusting the pH value, and performing neutralization reaction; (4) Aging, filtering, washing and drying to obtain alumina dry glue; (5) Uniformly mixing alumina dry glue, small-hole SB powder and sesbania powder, adding an adhesive to form a plastic body, extruding and molding, drying and roasting to obtain an alumina carrier, impregnating active metal, drying and roasting to obtain a fluidized bed catalyst, wherein the fluidized bed catalyst is prepared byThe catalyst prepared by the method has high strength and low abrasion.
CN101376829A discloses a fluidized bed hydrotreating catalyst and a preparation method thereof, the catalyst takes VIB group metal and VIII group metal as active components, and adopts an alumina carrier containing alumina fiber and a phosphorus auxiliary agent as a carrier, and the mechanical strength and the wear resistance of the catalyst are improved due to the addition of the alumina fiber and aluminum dihydrogen phosphate in the preparation process of the catalyst.
The fluidized bed hydrotreating catalyst prepared by the technology has better mechanical strength and wear resistance, can meet the requirements of a fluidized bed hydrotreating process, but has complex preparation process and higher production cost.
In the heavy residual oil hydrotreating process, metal impurities such as nickel, vanadium, iron and the like in the raw oil are easy to deposit in the added catalyst, so that the hydrotreating catalyst is deactivated. How to develop comprehensive utilization of heavy residual oil deactivated catalyst has gradually attracted attention.
CN111097440A discloses a regeneration method of a deactivated residual oil hydrotreating catalyst, which comprises the following steps: the method comprises the steps of carrying out charcoal burning and sulfur removal pretreatment on the deactivated residual oil hydrotreating catalyst, then carrying out unsaturated impregnation or saturated impregnation by using an acidic solution containing a complexing agent, carrying out impregnation treatment by using an alkaline solution, carrying out heat treatment in an ammonia-containing atmosphere, drying and roasting to obtain a regenerated hydrotreating catalyst. Although the method can utilize deposited metal impurities to make the deposited metal impurities be used as active metal in the regenerated catalyst and can improve the pore structure of the catalyst, the regeneration process is more complicated, the cost is higher, and the method is not beneficial to industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a boiling bed residual oil hydrogenation catalyst, which takes an inactivated boiling bed hydrogenation catalyst as a raw material, and the prepared catalyst has better wear resistance and catalytic activity through demetalization and strengthening treatment.
The preparation method of the boiling bed residual oil hydrogenation catalyst comprises the following steps:
(1) Roasting the deactivated catalyst to obtain a roasted material A;
(2) Performing demetalization treatment on the material A subjected to roasting treatment in the step (1), performing solid-liquid separation on the treated material, and drying the solid material to obtain a demetalization material B and a filtrate C;
(3) Dipping the demetallized material B in the step (2) by using a silicon-containing solution, and drying and roasting the dipped material to obtain a reinforced material D;
(4) Standing the filtrate C obtained in the step (2) at a low temperature, filtering, obtaining solid phase crystals which are ammonium vanadate after filtering, and concentrating the filtrate after filtering to obtain a solution E;
(5) And (4) impregnating the reinforced material D with the solution E in the step (4), and drying and roasting the impregnated material to obtain the fluidized bed hydrogenation catalyst.
In the method of the present invention, the deactivated catalyst in step (1) generally refers to a catalyst which is partially deactivated or fails to meet the reaction requirement due to deposition of heavy metals such as vanadium, iron, etc. and carbon deposition in the fluidized bed residue oil hydrotreating process, and the catalyst may be in a strip shape or a spherical shape, preferably a spherical shape; based on the weight of the catalyst (deactivated catalyst), the vanadium content is 5-25 percent calculated by oxide, the molybdenum content is 3-20 percent calculated by oxide, the nickel content is 2-15 percent calculated by oxide, and the alumina content is 40-80 percent calculated by oxide.
In the method of the present invention, the calcination temperature of the calcination treatment in step (1) is 500 to 850 ℃, preferably 550 to 750 ℃, and the calcination time is 6 to 12 hours, preferably 8 to 10 hours, depending on the carbon and sulfur contents of the final catalyst, so that the carbon content in the final catalyst is less than 0.5wt% as carbon element and the sulfur content is less than 0.2wt% as sulfur element. The calcination can be carried out in an oxygen-containing atmosphere with an oxygen content of 20v% to 100v%, such as an air atmosphere or an oxygen atmosphere, preferably, the calcination activation is carried out in an oxygen atmosphere.
In the method of the present invention, it is preferable to wash and extract the deactivated catalyst with an organic solvent before the deactivated catalyst is calcined to wash away the reaction materials on the surface and inside of the deactivated catalyst.
In the method, the demetallization treatment in the step (2) refers to a process of removing vanadium and molybdenum in the deactivated catalyst, and in the process, the roasting treatment material A, ammonium bicarbonate and water are mixed and then are subjected to sealing heat treatment. The mass ratio of the ammonium bicarbonate to the roasting treatment material A is 4:1-8:1, the mass ratio of the water consumption to the total mass of the ammonium bicarbonate and the roasting treatment material A is 1.5; the roasting material A, the ammonium bicarbonate and the water can be added and mixed in any order, for example, the water can be added into the mixture of the roasting material A and the ammonium bicarbonate, or the roasting material A can be immersed into the aqueous solution of the ammonium bicarbonate. The sealing heat treatment is carried out in a sealing device, preferably a high-pressure reaction kettle. The temperature of the sealing heat treatment is 120-180 ℃, preferably 130-170 ℃, and the treatment time is 4-10 hours, preferably 4-8 hours.
In the method, the drying temperature in the step (2) is 60-160 ℃, and the drying time is 4-8 hours.
In the method of the present invention, the silicon-containing solution in step (3) is an ethanol solution containing silicate ester, wherein the silicate ester is selected from one or more of methyl orthosilicate, ethyl orthosilicate and butyl orthosilicate.
In the method, the silicon-containing solution in the step (3) contains 1-4 wt% of silicon calculated by silicon dioxide based on the weight of the final catalyst, and the dosage of the silicon-containing solution is 15-25% of the saturated water absorption capacity of the demetallization material B.
In the method, the drying temperature in the step (3) is 60-160 ℃, the drying time is 4-8 hours, the roasting temperature is 550-750 ℃, preferably 650-750 ℃, and the roasting time is 4-10 hours.
In the method, the low-temperature standing temperature in the step (4) is 1-10 ℃, the standing time is 12-48h, and crystals are not precipitated in the solution during standing.
In the method of the invention, the concentration in the step (4) is generally concentrated by evaporation until the concentration of molybdenum in the solution is 8-20g/100mL calculated by oxide.
In the method of the present invention, the impregnation in step (5) may be an equal volume impregnation or an over volume impregnation, preferably an equal volume impregnation, and the impregnation time is 1 to 4 hours.
In the method, the drying temperature in the step (5) is 80-160 ℃, the drying time is 6-10 hours, and the roasting is carried out for 4-8 hours at the temperature of 450-550 ℃.
Compared with the prior art, the invention has the following advantages:
(1) The invention firstly carries out roasting treatment on the deactivated catalyst, the carbon deposited in the catalyst is removed through oxidation, the generated gas can play a role in reaming, on the other hand, the pore channels blocked by the deposited carbon are recovered, and the pore volume and the specific surface area of the catalyst are improved.
(2) When the deactivated catalyst is subjected to demetallization treatment, more than 75% of metal vanadium deposited in the deactivated catalyst is removed and dissolved in the solution, when the solution is kept stand at low temperature, vanadium is precipitated in the form of ammonium vanadate, valuable metal vanadium in the deactivated catalyst can be effectively recovered, and vanadium which is not dissolved in the deactivated catalyst can be used as a hydrogenation active component. The active metal molybdenum in the catalyst is completely dissolved into the alkaline solution during demetalization, and is recycled after concentration, so that the production cost of the catalyst is reduced. The active metal molybdenum is dissolved and then loaded, so that the dispersion degree of the active metal molybdenum is improved, the action of the active metal molybdenum and a carrier is improved, and the hydrogenation activity of the catalyst is improved.
(3) When the demetallization material is strengthened by the silicon-containing solution, the silicon in the solution forms a silicon dioxide shell layer on the surface of the catalyst, so that the strength and the wear resistance of the catalyst can be improved. In addition, due to the action of the silicon dioxide and the alumina carrier, the hydroxyl structure and the acid property of the surface of the carrier are regulated and controlled, so that the prepared catalyst has higher catalyst activity.
(4) In the preparation process of the catalyst, the demetallized material is used as a carrier, and molybdenum and vanadium in the deactivated catalyst are used as active metal components, so that the production cost of the catalyst is greatly reduced.
Detailed Description
The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples.
The BET method: application N 2 Physical adsorption-desorption characterization examples andcomparative example pore structure of the support, the operation was as follows: adopting ASAP-2420 type N 2 And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter is obtained according to a BJH model.
XRF characterization: analyzing the components of the sample, the target material Rh and the light path atmosphere by using a Japanese ZSX100e type X-ray fluorescence spectrometer: and (4) vacuum conditions.
The sulfur content in the oil is determined by adopting an SH/T0689-2000 standard method.
And the contents of Ni and V in the oil product are determined by adopting a GB/T34099-2017 standard method.
Catalyst attrition was determined using the ASTM D5757-2011 (2017) standard method.
Percent V + Ni removal rate = (raw material oil metal V + Ni content-product metal V + Ni content)/raw material oil metal V + Ni content is multiplied by 100 percent
Desulfurization rate% = (raw material oil sulfur content-product sulfur content)/raw material oil sulfur content x 100%.
Calculating the relative demetallization rate and the relative desulfurization rate: the demetalization rate and desulfurization rate of a certain catalyst are measured, the relative demetalization rate and relative desulfurization rate are respectively defined as 100%, and the impurity removal rate of other catalysts/the impurity removal rate of the defined catalyst multiplied by 100% is the relative impurity removal rate.
The deactivated catalyst adopted in the embodiment is the deactivated catalyst of an ebullated bed residual oil hydrogenation industrial device, oil on the surface of the catalyst is removed through extraction, and the catalyst is dried, and the catalyst after treatment comprises the following components: moO 3 ：12.0%，NiO：5.9%，V 2 O 5 ：15.2%，SiO 2 ：0.9%，Al 2 O 3 :57.4, C:7.1 percent. The catalyst is spherical particle with particle size of 0.2-1.0 mm.
Example 1
(1) Weighing 250 g of deactivated catalyst (subjected to extraction to remove oil on the surface of the catalyst and drying treatment) of the boiling bed residual oil hydrogenation industrial device, and roasting the deactivated catalyst for 8 hours at 650 ℃ in an oxygen atmosphere to obtain a roasted material A;
(2) 100 g of the roasted material A obtained in the step (1) is weighed, 530 g of ammonium bicarbonate and 1500 g of distilled water are added, the mixture is magnetically stirred for 30 minutes and then is transferred into an autoclave to be sealed and treated for 5.5 hours at the temperature of 145 ℃. And (3) carrying out liquid-solid separation on the treated material, and drying the separated solid material at 120 ℃ for 5 hours to obtain a demetallized material B. Standing the separated solution at 5 ℃ for 36 hours, filtering the solution after standing, obtaining ammonium vanadate as crystals after filtering, and evaporating and concentrating the solution after filtering until the concentration of molybdenum oxide is 11.7g/100mL to obtain a concentrated solution E;
(3) Weighing 50 g of demetallization material B (the saturated water absorption is 0.8 g/g) obtained in the step (2), placing the demetallization material B in a spray-dip rolling pot, carrying out unsaturated spray-dipping on the demetallization material B by using 9mL of ethyl orthosilicate ethanol solution (the content of silicon dioxide in the solution is 1 g) in a rolling state, drying the sprayed material B at 120 ℃ for 5 hours, and roasting at 650 ℃ for 6 hours to obtain a strengthened material D;
(4) Weighing 50 g of the reinforced material D obtained in the step (3), impregnating the reinforced material D with the concentrated solution E obtained in the step (2) by adopting an isovolumetric impregnation method, drying the impregnated material at 120 ℃ for 8 hours, and roasting the dried material at 450 ℃ for 6 hours to obtain the hydrogenation catalyst Cat1, wherein the properties of the catalyst are shown in Table 1.
Example 2
The same as example 1 except that the amount of ammonium hydrogencarbonate added during the demetallization treatment was 640 g, the temperature during the sealing treatment was 130 ℃ and the treatment time was 7.5 hours. When the silicon-containing solution is subjected to unsaturated spray-soaking, the dosage of an ethanol solution of ethyl orthosilicate is 8mL, the content of silicon dioxide in the solution is 1.2 g, and a hydrogenation catalyst Cat2 is prepared, wherein the properties of the catalyst are shown in Table 1.
Example 3
The same as example 1 except that the amount of ammonium hydrogencarbonate added during the demetallization treatment was 770 g, the temperature during the sealing treatment was 155 ℃ and the treatment time was 4.5 hours. When the silicon-containing solution is subjected to unsaturated spray-soaking, the dosage of the ethyl orthosilicate ethanol solution is 7mL, the content of silicon dioxide in the solution is 0.5 g, and the hydrogenation catalyst Cat3 is prepared, wherein the properties of the catalyst are shown in Table 1.
Example 4
The same procedure as in example 1 was repeated except that the amount of ammonium hydrogencarbonate added during the demetallization treatment was 410 g, the temperature during the sealing treatment was 165 ℃ and the treatment time was 6.5 hours. When the silicon-containing solution is subjected to unsaturated spray-soaking, the dosage of an ethanol solution of ethyl orthosilicate is 9.5mL, the content of silicon dioxide in the solution is 1.4 g, and a hydrogenation catalyst Cat4 is prepared, wherein the properties of the catalyst are shown in Table 1.
Comparative example 1
In the same manner as in example 1 except that the amount of ammonium hydrogencarbonate added was 150 g, a hydrogenation catalyst Cat-5 was obtained, the catalyst properties of which are shown in Table 1.
Comparative example 2
In the same way as example 1, except that the ammonium bicarbonate was changed to the same amount of ammonium carbonate, ammonium vanadate crystals were not precipitated in the alkali solution after the activation was observed, and a hydrogenation catalyst Cat-6 was obtained, and the properties of the catalyst are shown in Table 1.
Comparative example 3
The same procedure as in example 1, except that the temperature during the sealing treatment was 100 ℃ gave the hydrogenation catalyst Cat-7, the properties of which are shown in Table 1.
Comparative example 4
Similar to example 1, except that the catalyst was not subjected to impregnation strengthening treatment with a silicon-containing solution, a hydrogenation catalyst Cat-8 was obtained, and the catalyst properties are shown in Table 1.
TABLE 1 catalyst Properties
As can be seen from the data in Table 1, the ebullated-bed hydrogenation catalyst prepared by the method of the present invention has higher specific surface area and pore volume and lower abrasion.
Evaluation of catalytic performance:
the catalyst (Cat-1-Cat-8) after activation was evaluated for its catalytic performance by the following method:
the method comprises the following steps of (1) evaluating the catalytic performance of an activated catalyst Cat-1-Cat-8 on a fixed bed residual oil hydrogenation reaction device by taking certain vacuum residue as a raw material, wherein the content of metal (Ni + V) in the raw oil is 127 mu g/g, and the content of sulfur in the raw oil is 0.7wt%, and the reaction conditions are as follows: the reaction temperature is 385 ℃, the total reaction pressure is 8.5MPa, and the liquid hourly space velocity is 0.7 h -1 The volume ratio of hydrogen to oil is 800,after the reaction is carried out for 500 hours, the content of each impurity in the generated oil is determined, the impurity removal rate is calculated, and the evaluation result is shown in table 2.
TABLE 2 comparison of hydrogenation Performance of activated catalysts
It can be seen from the data in table 2 that the catalysts activated by the process of the present invention have higher hydrodemetallization and hydrodesulfurization activation compared to the comparative activated catalyst.
Claims (13)
1. The preparation method of the boiling bed residual oil hydrogenation catalyst is characterized by comprising the following steps: (1) Roasting the boiling bed residual oil hydrogenation catalyst which is partially inactivated or completely inactivated to obtain a roasting treatment material A; (2) Performing demetalization treatment on the roasting treatment material A in the step (1), performing solid-liquid separation on the treated material, and drying the solid material to obtain a demetalization material B and a filtrate C; (3) Dipping the demetallized material B in the step (2) by using a silicon-containing solution, and drying and roasting the dipped material to obtain a reinforced material D; (4) Standing the filtrate C obtained in the step (2) at a low temperature, filtering, obtaining solid phase crystals which are ammonium vanadate after filtering, and concentrating the filtrate after filtering to obtain a solution E; (5) And (5) impregnating the reinforced material D with the solution E obtained in the step (4), and drying and roasting the impregnated material to obtain the catalyst.
2. The method of claim 1, wherein: the inactivated catalyst in the step (1) is a catalyst which is partially inactivated or can not meet the reaction requirement due to deposition of heavy metal and carbon deposit in the boiling bed residual oil hydrotreating process, and is in a strip shape or a spherical shape; based on the weight of the deactivated catalyst, the content of vanadium is 5-25 percent calculated by oxide, the content of molybdenum is 3-20 percent calculated by oxide, the content of nickel is 2-15 percent calculated by oxide, and the content of alumina is 40-80 percent calculated by oxide.
3. The method of claim 1, wherein: the roasting temperature of the roasting treatment in the step (1) is 500-850 ℃, preferably 550-750 ℃, and the roasting time is 6-12 hours, preferably 8-10 hours, so that the carbon content of the final catalyst is lower than 0.5wt% calculated by carbon element, and the sulfur content is lower than 0.2wt% calculated by sulfur element.
4. The method of claim 1, wherein: the demetallization treatment in the step (2) is a process for removing vanadium and molybdenum in the deactivated catalyst, and in the process, the roasting treatment material A, ammonium bicarbonate and water are mixed and then subjected to sealing heat treatment.
5. The method of claim 4, wherein: the mass ratio of the ammonium bicarbonate to the roasting treatment material A is 4:1-8:1, the mass ratio of the water consumption to the total mass of the ammonium bicarbonate and the roasting treatment material A is 1.5.
6. The method of claim 4, wherein: the sealing heat treatment is carried out in a high-pressure reaction kettle, the temperature of the sealing heat treatment is 120-180 ℃, preferably 130-170 ℃, and the treatment time is 4-10 hours, preferably 4-8 hours.
7. The method of claim 1, wherein: the silicon-containing solution in the step (3) is an ethanol solution containing silicate ester, wherein the silicate ester is selected from one or more of methyl orthosilicate, ethyl orthosilicate and butyl orthosilicate.
8. The method of claim 1, wherein: in the silicon-containing solution in the step (3), the content of silicon is 1 to 4 weight percent of the weight of the final catalyst calculated by silicon dioxide, and the dosage of the silicon-containing solution is 15 to 25v percent of the saturated water absorption capacity of the demetallization material B.
9. The method of claim 1, wherein: the drying temperature in the step (3) is 60-160 ℃, the drying time is 4-8 hours, the roasting temperature is 550-750 ℃, and the roasting time is 4-10 hours.
10. The method of claim 1, wherein: and (4) keeping the low-temperature standing temperature at 1-10 ℃ for 12-48h.
11. The method of claim 1, wherein: and (4) concentrating until the concentration of molybdenum in the solution is 8-20g/100mL calculated by oxide.
12. The method of claim 1, wherein: the impregnation in the step (5) can be equal-volume impregnation or over-volume impregnation, and the impregnation time is 1-4 hours.
13. The method of claim 1, wherein: the drying temperature in the step (5) is 80-160 ℃, the drying time is 6-10 hours, and the roasting is carried out for 4-8 hours at the temperature of 450-550 ℃.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3705861A (en) * | 1969-06-03 | 1972-12-12 | Nippon Oil Co Ltd | Catalyst for the hydrogenation of distillation residuum-containing petroleum hydrocarbons |
| CA1224927A (en) * | 1982-09-24 | 1987-08-04 | Gale L. Hubred | Recovering metals from spent hydroprocessing catalysts |
| FR2895280A1 (en) * | 2005-12-22 | 2007-06-29 | Inst Francais Du Petrole | Hydrotreatment/hydroconversion of heavy hydrocarbon charge in fixed bed comprises reacting bed with hydrogenated gas containing liquid hydrocarbon in presence of catalyst |
| CN103769147A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103769122A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing hydro-treatment catalyst |
| CN105727977A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthetic gas methanation to substitute natural gas |
| CN108067244A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of spent catalyst recovery method |
| WO2018161952A1 (en) * | 2017-03-09 | 2018-09-13 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing hydrotreating catalyst by impregnation method |
| CN108970628A (en) * | 2018-08-08 | 2018-12-11 | 北京众智创新科技开发有限公司 | A kind of preparation method of boiling bed hydrogenation treatment catalyst |
| CN111686748A (en) * | 2019-03-13 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN111821994A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of demetallization catalyst |
| CN111821992A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN112746172A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
| CN113046117A (en) * | 2019-12-26 | 2021-06-29 | 中国石油化工股份有限公司 | Heavy oil hydrotreating process |
-
2021
- 2021-10-08 CN CN202111170072.7A patent/CN115957770A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3705861A (en) * | 1969-06-03 | 1972-12-12 | Nippon Oil Co Ltd | Catalyst for the hydrogenation of distillation residuum-containing petroleum hydrocarbons |
| CA1224927A (en) * | 1982-09-24 | 1987-08-04 | Gale L. Hubred | Recovering metals from spent hydroprocessing catalysts |
| FR2895280A1 (en) * | 2005-12-22 | 2007-06-29 | Inst Francais Du Petrole | Hydrotreatment/hydroconversion of heavy hydrocarbon charge in fixed bed comprises reacting bed with hydrogenated gas containing liquid hydrocarbon in presence of catalyst |
| CN103769147A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103769122A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing hydro-treatment catalyst |
| CN105727977A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthetic gas methanation to substitute natural gas |
| CN108067244A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of spent catalyst recovery method |
| WO2018161952A1 (en) * | 2017-03-09 | 2018-09-13 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing hydrotreating catalyst by impregnation method |
| CN108970628A (en) * | 2018-08-08 | 2018-12-11 | 北京众智创新科技开发有限公司 | A kind of preparation method of boiling bed hydrogenation treatment catalyst |
| CN111686748A (en) * | 2019-03-13 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN111821994A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of demetallization catalyst |
| CN111821992A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN112746172A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
| CN113046117A (en) * | 2019-12-26 | 2021-06-29 | 中国石油化工股份有限公司 | Heavy oil hydrotreating process |
Non-Patent Citations (4)
| Title |
|---|
| KADIEV K.M.: "Hydrogenation processing of oil wastes in the presence of ultrafine catalysts", 《PETROLEUM CHEMISTRY》, vol. 55, no. 8, 2 December 2015 (2015-12-02), pages 667 - 672, XP035580911, DOI: 10.1134/S0965544115080083 * |
| 刘喜来等: "FZC-24B型渣油加氢脱金属催化剂的开发", 《石化技术与应用》, no. 05, 10 September 2007 (2007-09-10), pages 391 - 394 * |
| 师新阁: "渣油热反应结焦和废催化剂再生研究", 《中国博士学位论文全文数据库》, 15 June 2020 (2020-06-15), pages 019 - 47 * |
| 马涛等: "失活渣油加氢脱金属催化剂再利用及钒回收技术研究", 《石油化工》, vol. 52, no. 08, 26 July 2023 (2023-07-26), pages 1060 - 1066 * |
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