CN114832865B - Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking - Google Patents
Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 53
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 10
- 239000003921 oil Substances 0.000 claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000000295 fuel oil Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 14
- 238000004945 emulsification Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 4
- 239000002199 base oil Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 3
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 3
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000000571 coke Substances 0.000 abstract description 6
- 238000004939 coking Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a molybdenum-based microemulsion catalyst applied to hydrocracking, which belongs to the technical field of slurry bed hydrogenation processes, and the prepared molybdenum-based microemulsion catalyst is applicable to the poor-quality heavy oil slurry bed hydrogenation process, can improve the light oil yield of the poor-quality heavy oil slurry bed hydrogenation process and inhibit coking rate, has the advantages of simplicity, lower cost and better stability, can reflect the stability of the microemulsion catalyst through the linear slope of a centrifugal stability parameter and turbidity ratio-time relation graph, and does not need stripping and dewatering, thereby reducing the cost and energy consumption; the molybdenum-based microemulsion catalyst prepared by the method has the advantages of good stability, smaller particle size distribution, good dispersing effect, high catalytic activity in the poor heavy oil slurry bed hydrogenation process and good coke inhibition capability, and can be highly dispersed in raw oil.
Description
Technical Field
The invention relates to the technical field of slurry bed hydrogenation processes, in particular to a preparation method of a molybdenum-based microemulsion catalyst applied to hydrocracking.
Background
The crude oil reserves in China are insufficient and are generally heavy, the residual oil (generally more than 500 ℃) accounts for a considerable proportion, and meanwhile, the continuously increased imported high-sulfur and high-metal crude oil also aggravates the inferior quality of the oil products in China, so the deep conversion of the heavy oil residual oil in the oil refining industry in China has to be regarded as a problem needing to be mainly overcome at the current node. The heavy oil hydrogenation process, i.e. the process of the chemical reaction of the raw oil and hydrogen under the action of the catalyst, has the advantages of high liquid yield, clean process and good product property. Therefore, the heavy oil hydrogenation process is an effective way for realizing efficient green conversion of the slag oil.
The dispersion of the catalyst in the slurry bed hydrogenation process is a key step, and the catalyst with fine particles can be uniformly and stably dispersed in the raw oil, so that the dosage of the catalyst is reduced, the cost is saved, and the catalyst has good catalytic activity. The slurry bed hydrogenation process generally adopts a dispersed catalyst, and the catalyst has the advantages of simple preparation process, higher catalytic activity and better catalytic selectivity.
The dispersion type catalyst generally comprises a water-soluble catalyst and an oil-soluble catalyst, and the oil-soluble catalyst has high hydrogenation activity and low coking rate, but has higher cost; the water-soluble catalyst has lower cost and better catalytic activity, but the shearing and dispersing process is more troublesome. The preparation method of the dispersed catalyst by using the microemulsion method has the advantages of simple preparation process, controllable particle size, better stability and higher catalytic activity, and has great significance for the dispersion and vulcanization process of the heavy oil slurry bed hydrogenation process and even the whole process.
Disclosure of Invention
The invention provides a preparation method of a molybdenum-based microemulsion catalyst applied to hydrocracking, which is applied to an inferior heavy oil slurry bed hydrogenation process, improves the light oil yield of the inferior heavy oil slurry bed hydrogenation process and inhibits the coking rate.
The specific technical scheme provided by the invention is as follows:
the invention provides a preparation method of a molybdenum-based microemulsion catalyst applied to hydrocracking, which is suitable for a poor-quality heavy oil slurry bed hydrogenation process, and comprises the following steps:
(1) Uniformly mixing the lipophilic surfactant and the hydrophilic surfactant according to a preset mass ratio, adding the mixture into the vacuum distillate, and continuously stirring the mixture for 5 to 10 minutes at a rotating speed of 1000 to 4000r/min in a constant-temperature magnetic stirrer with a preset emulsification temperature to obtain an oil phase part;
(2) Preparing molybdenum-metal salt solution with preset concentration by deionized water, heating and stirring at the same emulsification temperature until the metal salt is fully dissolved to obtain a water phase part;
(3) Gradually adding the water phase part into the oil phase part, and continuously stirring for 5-10 min at the rotating speed of 1000-4000 r/min to obtain the molybdenum-based microemulsion catalyst with uniform dispersion.
Optionally, the preset mass ratio of the lipophilic surfactant to the hydrophilic surfactant is 1-2.5:1, the sum of the mass of the lipophilic surfactant and the hydrophilic surfactant accounts for 10% -20% of the mass of the oil phase part, and the mass ratio of the sum of the mass of the lipophilic surfactant and the hydrophilic surfactant to the mass of the water phase part is 1-2:1.
Optionally, the lipophilic surfactant comprises one or more of span-60, span-65, span-80 and span-85, and the hydrophilic surfactant comprises one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, cetyltrimethylammonium bromide and tween-80.
Optionally, the vacuum distillate comprises one or more of straight run vacuum distillate, white oil and 400N base oil.
Optionally, the molybdenum-metal salt solution comprises one or more of ammonium molybdate tetrahydrate, sodium molybdate dihydrate and molybdenum phosphate.
Optionally, the total metal content of the molybdenum-based microemulsion catalyst added into the raw material is 150-1000 ug/g of the raw material.
The beneficial effects of the invention are as follows:
the invention provides a preparation method of a molybdenum-based microemulsion catalyst for hydrocracking, which comprises the steps of uniformly mixing and adding a lipophilic surfactant and a hydrophilic surfactant into vacuum distillate according to a certain mass ratio, and continuously stirring for 5-10 min at a rotating speed of 1000-4000 r/min in a constant-temperature magnetic stirrer with a set emulsification temperature to obtain an oil phase part; meanwhile, preparing molybdenum-metal salt solution with certain concentration by deionized water, heating and stirring at the same emulsification temperature until the metal salt is fully dissolved, and obtaining a water phase part; finally, gradually adding the water phase part into the oil phase, and then continuously stirring for 5-10 min to obtain the uniformly dispersed molybdenum-based microemulsion catalyst; the preparation method is simple, low in cost and good in stability, the stability of the microemulsion catalyst can be reflected by the linear slope of the centrifugal stability parameter and turbidity ratio-time relation diagram, and the molybdenum-based microemulsion catalyst prepared by the method does not need stripping for removing water, so that the cost and the energy consumption are reduced; the molybdenum-based microemulsion catalyst prepared by the method has the advantages of good stability, smaller particle size distribution, good dispersing effect, high catalytic activity in the poor heavy oil slurry bed hydrogenation process and good coke inhibition capability, and can be highly dispersed in raw oil.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of stability investigation relationship of a molybdenum-based microemulsion catalyst prepared in an embodiment of the invention;
FIG. 2 is a graph showing the particle size distribution of a molybdenum-based microemulsion catalyst prepared in accordance with an embodiment of the invention;
FIG. 3 is a graph showing the particle size distribution of a molybdenum-based microemulsion catalyst prepared in accordance with an embodiment of the present invention after sulfiding;
FIG. 4 is a graph showing the relationship between oil solubility and investigation of a molybdenum-based microemulsion catalyst prepared in the example of the present invention;
fig. 5 is an XRD pattern after sulfiding of the molybdenum-based microemulsion catalyst prepared in the example of the invention.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The molybdenum-based microemulsion catalyst is suitable for the poor-quality heavy oil slurry bed hydrogenation process, can improve the light oil yield and inhibit the coking rate, has simple process operation and low requirements on equipment and conditions, has good stability and small particle size distribution, can be highly dispersed in raw oil, and has high catalytic activity and good coking inhibition effect.
The invention provides a preparation method of a molybdenum-based microemulsion catalyst applied to hydrocracking, which is suitable for a poor-quality heavy oil slurry bed hydrogenation process, and comprises the following steps:
(1) Uniformly mixing the lipophilic surfactant and the hydrophilic surfactant according to a preset mass ratio, adding the mixture into the vacuum distillate, and continuously stirring the mixture for 5 to 10 minutes in a constant temperature magnetic stirrer with a preset emulsification temperature at a rotating speed of 1000 to 4000r/min to obtain an oil phase part.
(2) Preparing molybdenum-metal salt solution with preset concentration by deionized water, heating and stirring at the same emulsification temperature until the metal salt is fully dissolved to obtain a water phase part;
(3) Gradually adding the water phase part into the oil phase part, and continuously stirring for 5-10 min at the rotating speed of 1000-4000 r/min to obtain the molybdenum-based microemulsion catalyst with uniform dispersion.
Preferably, the preset mass ratio of the lipophilic surfactant to the hydrophilic surfactant is 1-2.5:1, the sum of the mass of the lipophilic surfactant and the hydrophilic surfactant accounts for 10% -20% of the mass of the oil phase part, and the mass ratio of the sum of the mass of the lipophilic surfactant and the hydrophilic surfactant to the mass of the water phase part is 1-2:1. The preset emulsification temperature is 35-45 ℃, and the preset concentration of the molybdenum-metal salt solution is 10-15% of the mass concentration ratio.
Further, the lipophilic surfactant adopted by the preparation method of the embodiment of the invention comprises one or more of span-60, span-65, span-80 and span-85, and the hydrophilic surfactant comprises one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, hexadecyl trimethyl ammonium bromide and tween-80. The vacuum distillate comprises one or more of straight run vacuum distillate, white oil and 400N base oil. The molybdenum-metal salt solution comprises one or more of ammonium molybdate tetrahydrate, sodium molybdate dihydrate and molybdenum phosphate.
Furthermore, the molybdenum-based microemulsion catalyst prepared by the preparation method of the embodiment of the invention is added into the raw material for use according to the proportion of 150-1000 ug/g of the total metal as the raw material.
The preparation method of the embodiment of the invention is simple, low in cost and good in stability, the stability of the microemulsion catalyst can be reflected by the linear slope of the centrifugal stability parameter and turbidity ratio-time relation diagram, and the molybdenum-based microemulsion catalyst prepared by the method does not need stripping for water removal, so that the cost and the energy consumption are reduced; the molybdenum-based microemulsion catalyst prepared by the method has the advantages of good stability, smaller particle size distribution, good dispersing effect, high catalytic activity in the poor heavy oil slurry bed hydrogenation process and good coke inhibition capability, and can be highly dispersed in raw oil.
The following is a detailed description of a method for preparing a molybdenum-based microemulsion catalyst for hydrocracking according to the present invention, with reference to specific examples.
Example 1
The preparation method of the molybdenum-based microemulsion catalyst applied to the inferior heavy oil slurry bed hydrogenation process comprises the following steps:
(1) Adding 5g of span-80 and 2.8g of sodium dodecyl benzene sulfonate into 40g of 400N base oil, and stirring in a constant temperature magnetic stirrer at 40 ℃ and a shear rate of 2000r/min for 10min to obtain an oil phase part;
(2) 0.61793g of ammonium molybdate tetrahydrate is added into 5g of deionized water, and stirred and dissolved at 40 ℃ to obtain a water phase part;
(3) Adding the fully dissolved water phase into the oil phase, stirring for 10min at 40 ℃ at a shear rate of 2000r/min, and cooling to room temperature to obtain the molybdenum-based microemulsion catalyst.
Among them, the stability parameters of the molybdenum-based microemulsion catalyst prepared in example 1 of the present invention are shown in the following table 1.
Table 1: stability parameters of molybdenum-based microemulsion catalysts
| Catalyst name | Centrifuge stability parameter/% | Relative absorbance/% | Turbidity ratio-time line slope |
| Example 1 | 99.23 | 95.57 | 9.0×10-6 |
Wherein, in Table 1
The invention is thatThe stability of the molybdenum-based microemulsion catalyst prepared in example 1 is examined and shown in FIG. 1. As can be seen from FIG. 1, in the range of 300 to 800nm, the absorbance value of the molybdenum-based microemulsion catalyst becomes smaller with the increase of wavelength, and therefore, the absorbance at 300nm and 800nm is selected as a turbidity ratio-time line, and turbidity reflects the change of the particle size and concentration of the microemulsion particles, so that the smaller the slope of the line, the smaller the change becomes, the more stable the microemulsion is, and the slope of the line is 9.0X10 -6 The microemulsion catalyst prepared in example 1 of the invention has good stability.
The particle size distribution of the molybdenum-based microemulsion catalyst prepared in example 1 of the invention is shown in FIG. 2. As can be seen from FIG. 2, the molybdenum-based microemulsion catalyst prepared by the preparation method has the advantages of narrow particle size distribution, average particle size of 6.78nm, clear and transparent appearance and good thermodynamic stability. The particle size distribution of the molybdenum-based microemulsion catalyst prepared in example 1 of the invention after vulcanization is shown in FIG. 3. In FIG. 3, it can be seen that the average particle size of the molybdenum-based microemulsion catalyst after vulcanization is 225.7nm, and the catalyst has good dispersibility in inferior heavy oil. The oil solubility of the molybdenum-based microemulsion catalyst prepared in example 1 of the invention is examined as shown in FIG. 4. The molybdenum-based microemulsion catalyst is respectively mixed with water, petroleum ether and kerosene according to a certain volume ratio, absorbance is measured after uniform oscillation, and a turbidity ratio-time relation diagram is made, the molybdenum-based microemulsion catalyst prepared by the embodiment of the invention is insoluble in water, and the linear slopes in petroleum ether and kerosene are respectively-2.97X10 -4 、2.33×10 -5 And the molybdenum-based microemulsion catalyst prepared in the embodiment 1 of the invention has better oil solubility because the catalyst is not layered after standing for a week.
The XRD pattern of the molybdenum-based microemulsion catalyst prepared in example 1 of the invention after sulfidation is shown in FIG. 5. In fig. 5, diffraction peaks at 14.1 °,33.8 °, 36.1 °, 39.7 °, 44.2 °, 49.5 °, 55.6 °,58.8 °, 59.0 °, 60.8 ° are MoS 2 Is a characteristic diffraction peak of (2). 2 theta is 14.1 DEG and MoS is near 2 002 peak of (C), 33.8 DEG is MoS 2 About 58.8℃for MoS 2 110 peak of (2). As shown in FIG. 5, the peak dispersion was not high in strength, indicating MoS 2 In the form of microcrystals.
Example 2
The molybdenum-based microemulsion catalyst prepared in example 1 above was used in a slurry bed hydrogenation process in Ma Rui Atmospheric Residuum (MRAR) and compared to the reaction under the same conditions using a blank reactor. Ma Rui Atmospheric Residuum (MRAR) properties are shown in table 2 with the reaction conditions: the reaction temperature is 420 ℃, the initial pressure is 8MPa, the reaction time is 60min, the catalyst addition amount is 500ug/g (based on the total metal amount), and the vulcanizing agent is 1000ug/g; the reaction results are shown in Table 3.
Table 2: composition and Property analysis of Ma Rui atmospheric residuum
Table 3: ma Rui distribution of reaction products of atmospheric residuum hydrogenation co-refining
And calculating the light oil yield (I value) per unit coke according to the light oil yield and the coke yield, wherein the hydrogenation and coke inhibition activity of the catalyst are stronger when the I value is larger. As can be seen from Table 3, compared with the blank experiment, the molybdenum-based microemulsion catalyst prepared in example 1 of the invention has low coking rate of the reaction system, relatively less gas-phase products and higher catalytic activity.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments of the present invention without departing from the spirit or scope of the embodiments of the invention. Thus, if such modifications and variations of the embodiments of the present invention fall within the scope of the claims and the equivalents thereof, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A method for preparing a molybdenum-based microemulsion catalyst applied to hydrocracking, wherein the molybdenum-based microemulsion catalyst is suitable for a poor heavy oil slurry bed hydrogenation process, and is characterized by comprising the following steps:
(1) Uniformly mixing an oleophylic surfactant and a hydrophilic surfactant according to a preset mass ratio, adding the mixture into vacuum distillate, and continuously stirring the mixture for 5 to 10 minutes at a rotating speed of 1000 to 4000r/min in a constant-temperature magnetic stirrer with a preset emulsification temperature to obtain an oil phase part, wherein the preset emulsification temperature is 35 to 45 ℃, the preset mass ratio of the oleophylic surfactant to the hydrophilic surfactant is 1 to 2.5:1, and the mass sum of the oleophylic surfactant and the hydrophilic surfactant accounts for 10 to 20 percent of the mass of the oil phase part;
(2) Preparing a molybdenum-metal salt solution with preset concentration by deionized water, heating and stirring the solution at the same emulsification temperature until the metal salt is fully dissolved to obtain a water phase part, wherein the preset concentration of the molybdenum-metal salt solution is 10% -15% by mass concentration, and the mass ratio of the sum of the mass of the lipophilic surfactant and the mass of the hydrophilic surfactant to the mass of the water phase part is 1-2:1;
(3) Gradually adding the water phase part into the oil phase part, and continuously stirring at a rotating speed of 1000-4000 r/min for 5-10 min to obtain the molybdenum-based microemulsion catalyst with uniform dispersion.
2. The preparation method according to claim 1, wherein the lipophilic surfactant comprises one or more of span-60, span-65, span-80 and span-85, and the hydrophilic surfactant comprises one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, cetyltrimethylammonium bromide and tween-80.
3. The method according to claim 1, wherein the vacuum distillate comprises one or more of straight run vacuum distillate, white oil, and 400N base oil.
4. The method of claim 1, wherein the molybdenum-metal salt solution comprises one or more of ammonium molybdate tetrahydrate, sodium molybdate dihydrate, and molybdenum phosphate.
5. The method according to claim 1, wherein the total amount of metal added to the raw material of the molybdenum-based microemulsion catalyst is 150 to 1000 μg/g of the raw material.
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