CN114874809B - Low-pressure hydrodesulfurization reaction system and reaction method - Google Patents
Low-pressure hydrodesulfurization reaction system and reaction method Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 86
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000007789 gas Substances 0.000 claims abstract description 42
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 17
- 230000023556 desulfurization Effects 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003921 oil Substances 0.000 description 39
- 239000007791 liquid phase Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002283 diesel fuel Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention provides a low-pressure hydrodesulfurization reaction system and a reaction method, wherein the reaction system comprises a hydrogen feeding unit, a raw oil feeding unit, a raw material preheating unit, a gas dispersing unit, a low-pressure reaction unit, a condensing unit and a separating unit; the hydrogen feeding unit comprises a hydrogen feeding branch; the gas dispersing unit comprises a gas disperser; the gas disperser comprises at least 2 types of dispersing heads; the diameters of pore canal of each type of dispersing heads are different from each other, and the distribution distance can be adjusted according to the requirement; the dispersing head is correspondingly connected with the hydrogen feeding branch; the reaction system can adjust proper reaction conditions and further strengthen the reaction rate of raw oil hydrogenation by optimizing the internal structure of the gas disperser aiming at different raw oil types, so that the raw oil hydrogenation product achieves the effect of deep desulfurization under the mild hydrogenation condition, and has certain economic benefit.
Description
Technical Field
The invention belongs to the technical field of oil refining and chemical industry, and particularly relates to a low-pressure hydrodesulfurization reaction system and a reaction method.
Background
Sulfur oxides SO are generated after sulfides in diesel oil are combusted by an engine x The waste water is discharged into the atmosphere, so that acid rain is caused, the ozone layer is destroyed, and the greenhouse effect is generated. Meanwhile, sulfides in diesel oil have great influence on the service life of an engine, and active sulfides such as mercaptan and the like have corrosion effect on metals. Therefore, in order to meet the continuous and strict environmental protection requirements of the country and improve the service performance of the oil, the quality upgrading steps of the gasoline and diesel oil of the country are quickened, and the sulfur content of the emission standard implemented at the present stage is 10ppm. The quality of the processed crude oil in China is not high, the content of heavy components is high, the sulfur content of raw oil is high, the stability and the service efficiency of a diesel product are affected by components such as sulfur, nitrogen, aromatic hydrocarbon and colloid, and the quality of the diesel is required to be improved through hydrofining. The diesel hydrofining catalyst can meet the production requirement after several generations of updating, but in recent years, breakthrough technical achievements are reported, so that a plurality of students seek more effective cost-reducing and synergy means in the hydrogenation process.
In order to improve the hydrofining desulfurization effect of diesel oil and greatly reduce the production cost, a liquid phase hydrogenation technology is catalyzed from the traditional trickle bed hydrogenation technology, namely, a liquid phase is a continuous phase, hydrogen is a disperse phase, and hydrogen dissolved in the liquid phase is utilized to carry out hydrogenation reaction on the surface of a catalyst. The liquid phase hydrogenation generally adopts a mode of directly mixing hydrogen and raw materials, the mode forms bubbles with large diameters and most of bubbles above millimeter level, and the bubbles are easy to coalesce and form large bubbles in the flowing process of the bulk catalyst bed layer, so that the mass transfer specific surface area is reduced, the dissolution rate of the hydrogen in an oil phase is reduced, and the hydrogenation reaction rate is limited. Therefore, the multi-point hydrogen supplementing or the circulating oil increasing is needed to increase the dissolved hydrogen in the liquid phase to maintain the hydrogenation reaction rate, and the excessive unreacted hydrogen is also needed to be separated and discharged. Different technologies are correspondingly developed on solving the problem at present in China.
CN111068588A discloses a diesel oil ultra-deep desulfurization device and a diesel oil hydrogenation reaction system. In the method, a plurality of U-shaped tubular reactors are connected in series behind a fixed bed hydrogenation reactor, and adjacent reactors are connected through arc-shaped tubes. The straight pipe section in the U-shaped tubular reactor is divided into a hydrogenation reaction section, a stripping section and a horizontal section which is a hydrogen injection section. Its main function is to react H produced 2 S、NH 3 And the gas is removed from the reaction system, so that the hydrogenation reaction rate is improved. However, the plurality of U-shaped tubular reactors of the device are connected in series, so that the process flow is increased, the structure is complex, the operation is not facilitated, meanwhile, the hydrogenation catalyst is filled in the U-shaped tubular reactors, if the process condition is improperly controlled, the pressure drop is easily generated, and the risk of unplanned shutdown of the device is increased.
CN111073688A discloses a diesel deep desulfurization hydrotreating method. In the method, a catalyst combination grading scheme is utilized to carry out desulfurization of diesel products. The average reaction temperature in the method is 330-450 ℃, the partial pressure of the reaction hydrogen is 8.0-20.0MPa, the liquid hourly space velocity is 0.15-3.0h < -1 >, and the hydrogen-oil ratio is 300-1500. The method needs to prepare 3 kinds of catalysts with different sulfuration degrees, and then the catalysts are filled in a grading mode, so that the steps are complex and complicated. The reaction temperature and the reaction pressure are high, the conditions are severe, the operation cost of the device is increased to a certain extent, and the device is not suitable for long-period operation.
CN111359542a discloses a micro-interface enhanced hydrofining reaction system and method. The method also mixes the hydrogen micro-bubbles with the diesel oil to increase the area of the gas-liquid two-phase boundary, thereby strengthening the mass transfer reaction process. The diameter of hydrogen micro-bubbles is between 1 micron and 1 millimeter, and the hydrogenation reaction pressure is 1-14MPa. CN110396425a discloses a device and a method for enhancing liquid-phase circulation hydrogenation by micro-interface. The method adopts a microbubble generator to mix hydrogen with the oil phase in a large number of microbubble states, and supplements hydrogen into the oil phase through a large number of suspended microbubbles, so that circulating hydrogen is eliminated, high pressure is utilized to improve hydrogen solubility, and hydrogen is supplemented. After the hydrogenation reaction is finished, a part of the product enters a gas-liquid separator, and a part of the product is circulated to a micro-bubble generator for recycling hydrogenation reaction. The hydrogenation reaction pressure of the method is 2-10MPa. The 2 patents mentioned above enhance the liquid phase hydrogenation process by micro-interfaces, but still suffer from the following disadvantages: (1) The diameter of hydrogen microbubbles in the diesel liquid phase is still larger and the distribution is not uniform; (2) The large bubbles are prone to generate local liquid phase short circuits in the gaps between the catalyst bed layers, which adversely affects the efficiency of the diesel hydrofining reaction.
In summary, how to provide a hydrodesulfurization reaction system and a reaction method, which enable a diesel liquid phase and hydrogen microbubbles with uniform size to form a quasi-homogeneous phase flow, thereby improving the reaction rate of diesel hydrofining, achieving a better desulfurization effect under a gentler hydrogenation condition, and becoming the current problem to be solved urgently.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a low-pressure hydrodesulfurization reaction system and a reaction method, wherein the reaction system can be suitable for different raw oil types by optimizing the internal structure of a gas disperser, can further strengthen the reaction rate of raw oil hydrofining, and can enable the hydrogenated product of the raw oil to achieve the effect of deep desulfurization under the milder hydrogenation condition.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a low-pressure hydrodesulfurization reaction system, which comprises a feeding unit, a raw material preheating unit, a gas dispersing unit, a low-pressure reaction unit, a condensing unit and a separating unit which are connected in sequence;
the feeding unit comprises a hydrogen feeding unit and a raw oil feeding unit, and the hydrogen feeding unit and the raw oil feeding unit are respectively and independently connected with the gas dispersing unit;
the hydrogen feeding unit further comprises a hydrogen feeding branch;
the gas dispersing unit comprises a gas disperser;
the gas disperser comprises at least 2 types of dispersing heads, such as 2, 3, 4, 5 or 6, but is not limited to the recited values, and other non-recited values in the range are equally applicable and are arranged in parallel.
The diameters of the pore canal of each type of dispersing head are different from each other;
the number of the hydrogen feeding branches is equal to that of the dispersing heads, and each dispersing head is independently connected with the corresponding hydrogen feeding branch.
According to the invention, the dispersing heads of various types are arranged in the gas disperser in parallel, the structure and the distribution interval of the dispersing heads are optimized, the quasi-phase flow of hydrogen and raw oil is realized, and meanwhile, the proper reaction conditions (namely, optimal gas-liquid ratio, micro bubbles with optimal size and the like) can be adjusted for different raw oil types, so that the effect of strengthening the hydrogenation reaction process is achieved, the hydrogenation condition is greatly eased, and the purpose of deep desulfurization is realized under lower pressure. The reaction system described in the present invention is referred to as a system device.
According to the invention, each dispersing head is connected with the corresponding hydrogen feeding branch, and when the gas flow is required to be reduced or increased, the optimal gas-liquid ratio can be adjusted while ensuring the optimal micro-bubble size by closing or opening the number and the types of the dispersing heads.
In the present invention, in order to distinguish different types of dispersion heads, the first dispersion head, the second dispersion head, the third dispersion head, the fourth dispersion head, and the like are named respectively.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the hydrogen feeding unit comprises a hydrogen compressor, a hydrogen filter and a hydrogen buffer tank which are sequentially connected.
Preferably, the raw oil feeding unit comprises a raw oil feeding pump and a liquid filter which are connected in sequence.
Preferably, the raw oil feed pump includes any one of a centrifugal pump, a reciprocating pump, or a diaphragm pump.
In a preferred embodiment of the present invention, the impurity particle size of the hydrogen gas filter is in the range of 0.1 to 100. Mu.m, for example, 0.1. Mu.m, 1. Mu.m, 10. Mu.m, 20. Mu.m, 50. Mu.m, 80. Mu.m, 100. Mu.m, etc., but the hydrogen gas filter is not limited to the recited values, and other non-recited values are applicable within the range of the recited values.
Preferably, the liquid filter filters impurities having a particle size in the range of 1-1000 μm, for example 1 μm, 5 μm, 1000 μm, 10 μm, 50 μm, 100 μm, 200 μm, 400 μm, 600 μm, 800 μm or 1000 μm, etc., but are not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the raw material preheating unit comprises a liquid preheater and a hydrogen preheater, wherein the liquid preheater is connected with the liquid feeding unit, and the hydrogen preheater is connected with the hydrogen feeding unit.
As a preferable technical scheme of the invention, the disperser is a micro-bubble gas-liquid mixing device.
Preferably, each type of dispersion head comprises at least 1, for example 1, 2, 3, 4, 5 or 6, etc., but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the distribution pitch of the dispersing heads is any one or a combination of at least two of 3cm, 6cm, 9cm, 12cm or 15cm, for example, a combination of 3cm and 6cm, a combination of 3cm, 9cm and 15cm, or the like.
In the invention, the horizontal distribution condition depends on the size of bubbles and influences the state of the bubbles, and the optimal number of bubbles can not be achieved when the low-pressure hydrodesulfurization reaction is performed, for example, the bubbles are too much arranged; if too dense bubbles are installed there is a risk of coalescence.
As a preferred embodiment of the present invention, the low pressure reaction unit includes a low pressure reactor.
Preferably, the inside of the low pressure reactor is filled with a hydrofining catalyst.
Preferably, the hydrofinishing catalyst comprises a particulate catalyst or a monolithic catalyst.
Preferably, the bed of monolithic catalyst is internally provided with channels that are mutually parallel and perpendicular.
Preferably, the cross-sectional shape of the channel includes any one of regular triangle, regular quadrangle, regular hexagon, or circle.
In a second aspect, the present invention provides a low pressure hydrodesulphurisation reaction process carried out using a reaction system as described in the first aspect,
in a third aspect, the present invention provides the use of a composite separator as described above, the reaction method comprising the steps of:
the hydrogen and the raw oil are respectively filtered and preheated and then are led into a gas disperser, generated hydrogen microbubbles and the raw oil form quasi-homogeneous fluid, and are led into a low-pressure reaction unit for reaction, condensed after the reaction, and then enter a separation unit for gas-liquid separation, so that desulfurization of the raw oil is realized;
the pressure of the reaction is 1 to 5MPa, for example, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The reaction method can realize deep desulfurization of the raw oil under 5MPa (the difference between the maximum reaction pressure and the minimum reaction pressure is not more than 4 MPa), greatly eases hydrogenation reaction conditions, reduces energy consumption, has better safety and is beneficial to industrial production.
As a preferred embodiment of the present invention, the preheating temperature of the hydrogen gas is 20 to 350 ℃, for example, 20 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃,300 ℃, 350 ℃, etc.; the preheating temperature of the raw oil is 20 to 350 ℃, for example, 20 ℃, 40 ℃, 80 ℃, 120 ℃, 160 ℃, 220 ℃, 280 ℃, 320 ℃, or the like, and the selection of the above values is not limited to the listed values, and other values not listed in the respective value ranges are equally applicable.
As a preferred embodiment of the present invention, the hydrogen microbubbles have a diameter of any one or a combination of at least two of 0.1 to 10 μm, 10 to 50 μm, 50 to 100 μm, 100 to 200 μm, 200 to 300 μm, 300 to 400 μm, 400 to 500 μm, or 500 to 600 μm, and typical but non-limiting examples of the combination are: 0.1-10 μm and 10-50 μm, 300-400 μm and 400-500 μm, etc.
As a preferred embodiment of the present invention, the temperature of the reaction is 150 to 500℃such as 150℃200℃250℃300℃350℃400℃450℃500℃or the like; space velocity of 0.5-5h -1 For example 0.5h -1 、1h -1 、2h -1 、3h -1 、4h -1 Or 5h -1 Etc.; the hydrogen to oil ratio of 200 to 500:1, e.g., 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, etc., is not limited to the recited values, and other non-recited values within the respective ranges are equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) The reaction system can realize that gas-phase hydrogen forms quasi-homogeneous phase flow of micro-bubbles with uniform size in liquid-phase diesel by optimizing the structure of a disperser, and the quasi-homogeneous phase flow is matched with the integral catalyst pore channel structure in a hydrogenation reactor, thereby greatly strengthening the hydrodesulfurization process of the diesel, improving the refining reaction rate, leading the sulfur content in the product to be below 56mg/kg, even to be 5mg/kg, and leading the desulfurization rate to be 97.15 percent and to be up to 99.81 percent.
(2) The reaction system provided by the invention can realize deep desulfurization, greatly reduce the severity of reaction conditions, improve the safety of reaction and have certain economic benefits.
Drawings
FIG. 1 is a schematic diagram of a reaction system for strengthening the hydrodesulfurization and decolorizing process according to embodiment 1 of the present invention.
Fig. 2 is a schematic diagram showing the distribution of gas dispersing heads in the enhanced reaction system for hydrodesulfurization and decolorizing process according to embodiment 1 of the present invention.
Fig. 3 is a schematic diagram showing the distribution of gas dispersing heads in the enhanced reaction system for hydrodesulfurization and decolorizing process according to embodiment 2 of the present invention.
Fig. 4 is a schematic diagram showing the distribution of gas dispersing heads in the enhanced reaction system for hydrodesulfurization and decolorizing process according to embodiment 3 of the present invention.
The device comprises a 1-raw oil inlet, a 2-raw oil feed pump, a 3-liquid filter, a 4-liquid preheater, a 5-hydrogen inlet, a 6-hydrogen compressor, a 7-hydrogen filter, an 8-hydrogen buffer tank, a 9-hydrogen preheater, a 10-gas disperser, a 101-first dispersing head 101, a 102-second dispersing head, a 103-third dispersing head, a 11-low pressure reactor, a 12-condenser, a 13-oil-gas separator, a 14-separated gas phase outlet and a 15-hydrogenated liquid phase product outlet.
The arrow direction represents the flow direction.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
In one specific embodiment, the invention provides a low-pressure hydrodesulfurization reaction system and a reaction method, wherein the reaction system comprises a feeding unit, a raw material preheating unit, a gas dispersing unit, a low-pressure reaction unit, a condensing unit and a separating unit which are connected in sequence;
the feeding unit comprises a hydrogen feeding unit and a raw oil feeding unit, and the hydrogen feeding unit and the raw oil feeding unit are respectively and independently connected with the gas dispersing unit;
the hydrogen feeding unit further comprises a hydrogen feeding branch;
the gas dispersion unit includes a gas disperser 10;
the gas disperser 10 comprises at least 2 types of dispersing heads, wherein each type of dispersing head comprises at least 1 dispersing head and is arranged in parallel; the diameters of the pore canal of each type of dispersing head are different from each other; the distribution interval of the dispersing heads is any one or the combination of at least two of 3cm, 6cm, 9cm, 12cm or 15 cm.
The number of the hydrogen feeding branches is equal to that of the dispersing heads, and each dispersing head is independently connected with the corresponding hydrogen feeding branch.
Further, the hydrogen feeding unit comprises a hydrogen compressor 6, a hydrogen filter 7 and a hydrogen buffer tank 8 which are sequentially connected, the raw oil feeding unit comprises a raw oil feeding pump 2 and a liquid filter 3 which are sequentially connected, and the raw oil feeding pump 2 is a centrifugal pump.
Further, the impurity particle size range of the hydrogen filter 7 is 0.1-100 μm; the impurity particle size of the liquid filter 3 is in the range of 1-1000 μm.
Further, the raw material preheating unit comprises a liquid preheater 4 and a hydrogen preheater 9, wherein the liquid preheater 4 is connected with the liquid feeding unit, and the hydrogen preheater 9 is connected with the hydrogen feeding unit.
Further, the gas disperser 10 is a micro-bubble gas-liquid mixing device.
Further, the low pressure reaction unit comprises a low pressure reactor 11, the inside of the low pressure reactor 11 is filled with a hydrofining catalyst, the hydrofining catalyst comprises a granular catalyst or a monolithic catalyst, channels which are parallel and vertical to each other are arranged in a bed layer of the monolithic catalyst, and the cross section shape of the channels comprises any one of regular triangle, regular quadrangle, regular hexagon or circle.
Further, the separation unit includes an oil separator 13.
The reaction method carried out by adopting the reaction system comprises the following steps:
filtering hydrogen and raw material oil respectively, independently preheating to 20-350deg.C, introducing into gas disperser 10, generating hydrogen microbubbles (0.1-10 μm, 10-50 μm, 50-100 μm, 100-200 μm, 200-300 μm, 300-400 μm, 400-500 μm or 500-600 μm or their combination), forming quasi-homogeneous fluid with raw material oil, introducing into low-pressure reactor 11, and reacting at 150-500deg.C under 1-5MPa at airspeed of 0.5-5h -1 Hydrogen-oil ratio of 200-500:1), after reaction, entering a condenser 12, condensing, then introducing into a separation unit for gas-liquid separation, and separating H 2 S gas and unreacted hydrogen are discharged from the top of the oil-gas separator 13, and the hydrogenated liquid phase product flows out from the bottom, so that deep desulfurization of the raw oil is realized.
The following are exemplary but non-limiting examples of the invention:
examples 1-7 provide a low pressure hydrodesulfurization reaction system and a reaction method, respectively, and the detailed parameters of the reaction system in each example are shown in table 1 based on the reaction system in the specific embodiment; based on the reaction method in the specific embodiment, the specific parameter conditions of the reaction method and the test results of sulfur content, nitrogen content and chromaticity of the product in the hydrogenated product in each example are shown in table 2.
The schematic structure of the reaction system of embodiment 1 is shown in fig. 1, the schematic distribution of the gas dispersing heads of embodiment 1 is shown in fig. 2, the schematic distribution of the gas dispersing heads of embodiment 2 is shown in fig. 3, and the schematic distribution of the gas dispersing heads of embodiment 3 is shown in fig. 4.
TABLE 1
TABLE 2
Wherein, the number of the dispersion heads is 3/4/5, which means that "the first dispersion heads 101 have 3, the second dispersion heads 102 have 4, and the third dispersion heads 103 have 5".
Comparative example 1:
this comparative example provides a low pressure hydrodesulfurization reaction system, which is different from that of example 1 in that:
the hydrogen feeding unit had only 1 hydrogen feeding main line, and the gas disperser included only 1 type of dispersing heads (dispersing heads with diameters of 30 to 80 μm for generating microbubbles) in an amount of 12, and the distribution positions of the 12 dispersing heads in the dispersion were the same as in example 1.
The same effects as in example 1 can be achieved when the reaction conditions in example 1 are used to carry out the catalytic diesel hydrogenation reaction using the above reaction system.
However, when the hydrogenation reaction is performed on the raw oil (catalytic diesel oil and straight-run diesel oil) in the embodiment 5, because the required hydrogen oil is relatively low, the air inflow of hydrogen is reduced, the total hydrogen feeding valve is required to be adjusted to be small, the number of micro bubbles with corresponding size can be obviously reduced, and the hydrogenation strengthening effect is not obvious any more.
Therefore, the system device can ensure the optimal hydrogen-oil ratio and the reasonable size of hydrogen microbubbles at the same time, thereby strengthening the hydrodesulfurization and decoloration effects.
Comparative example 2:
this comparative example provides a conventional trickle bed hydrogenation reactor and hydrogenation process charged with the same hydrofinishing catalyst as in example 2 and employing the same feedstock as in example 2, the reaction conditions of the hydrogenation process being as follows: the reaction temperature is 340 ℃, the reaction pressure is 3.4MPa, and the volume space velocity is 1.5h -1 The hydrogen-to-oil ratio was 275:1.
The sulfur content of the hydrogenated product obtained by the process is 156mg/kg, and the desulfurization rate is only 97.2%.
It can be seen from the above examples and comparative examples that the reaction system of the invention can realize that gas phase hydrogen forms quasi-phase flow of micro-bubbles with uniform size in liquid phase diesel by optimizing the structure of the disperser, and then greatly intensifies the hydrodesulfurization process of diesel by matching with the integral catalyst pore canal structure in the hydrogenation reactor, thereby improving the refining reaction rate, leading the sulfur content in the product to be below 56mg/kg, even to be 5mg/kg, and the desulfurization rate to be 97.15 percent, and to be 99.81 percent at most; the reaction system greatly reduces the severity of reaction conditions while realizing deep desulfurization, improves the safety of reaction, and has certain economic benefit.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for operation of the present invention, addition of auxiliary operations, selection of specific modes, etc., are intended to fall within the scope of the present invention and the scope of the disclosure.
Claims (4)
1. The low-pressure hydrodesulfurization reaction method is characterized by adopting a low-pressure hydrodesulfurization reaction system, wherein the reaction system comprises a feeding unit, a raw material preheating unit, a gas dispersing unit, a low-pressure reaction unit, a condensing unit and a separating unit which are connected in sequence;
the feeding unit comprises a hydrogen feeding unit and a raw oil feeding unit, and the hydrogen feeding unit and the raw oil feeding unit are respectively and independently connected with the gas dispersing unit;
the hydrogen feeding unit further comprises a hydrogen feeding branch;
the gas dispersing unit comprises a gas disperser;
the gas disperser at least comprises 2 types of dispersing heads and is arranged in parallel; the diameters of the pore canal of each type of dispersing head are different from each other; each type of dispersing head comprises at least 1 dispersing head, and the distribution interval of the dispersing heads is any one or the combination of at least two of 3cm, 6cm, 9cm, 12cm or 15 cm;
the number of the hydrogen feeding branches is equal to that of the dispersing heads, each dispersing head is independently connected with the corresponding hydrogen feeding branch, and when the gas flow is required to be reduced or increased, the adjustment of the optimal gas-liquid ratio is realized by closing or opening the number and the types of the dispersing heads required, namely, the optimal micro-bubble size is ensured;
the hydrogen feeding unit comprises a hydrogen compressor, a hydrogen filter and a hydrogen buffer tank which are sequentially connected;
the raw oil feeding unit comprises a raw oil feeding pump and a liquid filter which are sequentially connected;
the particle size range of the impurities filtered by the hydrogen filter is 0.1-100 mu m;
the particle size range of the impurities filtered by the liquid filter is 1-1000 mu m;
the raw material preheating unit comprises a liquid preheater and a hydrogen preheater, wherein the liquid preheater is connected with the raw material oil feeding unit, and the hydrogen preheater is connected with the hydrogen feeding unit;
the low-pressure reaction unit comprises a low-pressure reactor;
the inside of the low-pressure reactor is filled with a hydrofining catalyst;
the hydrofining catalyst comprises a granular catalyst or a monolithic catalyst;
channels which are parallel and vertical to each other are arranged in the bed layer of the integral catalyst;
the cross section shape of the channel comprises any one of regular triangle, regular quadrangle, regular hexagon or circle;
the reaction method comprises the following steps:
the hydrogen and the raw oil are respectively filtered and preheated and then are led into a gas disperser, generated hydrogen microbubbles and the raw oil form quasi-homogeneous fluid, and are led into a low-pressure reaction unit for reaction, condensed after the reaction, and then enter a separation unit for gas-liquid separation, so that desulfurization of the raw oil is realized;
the pressure of the reaction is 1-5MPa.
2. The reaction method according to claim 1, wherein the preheating temperature of the hydrogen gas is 20 to 350 ℃ and the preheating temperature of the raw oil is 20 to 350 ℃.
3. The reaction method according to claim 1, wherein the hydrogen microbubbles have a diameter of any one or a combination of at least two of 0.1 to 10 μm, 10 to 50 μm, 50 to 100 μm, 100 to 200 μm, 200 to 300 μm, 300 to 400 μm, 400 to 500 μm, or 500 to 600 μm.
4. The process according to claim 1, wherein the reaction is carried out at a temperature of 150 to 500℃and a space velocity of 0.5 to 5 hours -1 The hydrogen-oil ratio is 200-500:1.
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