CN116099402B - Liquid phase hydrogenation strengthening hydrogen mixing device and method - Google Patents
Liquid phase hydrogenation strengthening hydrogen mixing device and method Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 173
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 173
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 138
- 239000007791 liquid phase Substances 0.000 title claims abstract description 89
- 238000005728 strengthening Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 155
- 239000000919 ceramic Substances 0.000 claims abstract description 154
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 239000007789 gas Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 150000002431 hydrogen Chemical class 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- 230000009471 action Effects 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 13
- 238000010008 shearing Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 5
- 239000004530 micro-emulsion Substances 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 238000012546 transfer Methods 0.000 abstract description 14
- 239000003921 oil Substances 0.000 description 73
- 239000000047 product Substances 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010724 circulating oil Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101000583474 Homo sapiens Phosphatidylinositol-binding clathrin assembly protein Proteins 0.000 description 1
- 102100031014 Phosphatidylinositol-binding clathrin assembly protein Human genes 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a liquid-phase hydrogenation strengthening hydrogen mixing device and a method. One end of the shell is provided with a liquid inlet, the bottom is provided with an air inlet, the other end is provided with a gas-liquid mixing outlet; the porous ceramic membrane is arranged in the shell, two ends of the porous ceramic membrane are provided with openings, the openings are respectively communicated with the liquid inlet and the gas-liquid mixing outlet, and the side wall of the porous ceramic membrane is communicated with the gas inlet; the inside of the porous ceramic membrane is provided with a plurality of ceramic membrane baffles which are arranged in a staggered way up and down. The liquid phase hydrogenation strengthening hydrogen mixing device can improve the hydrogen mixing amount of the oil product in the liquid phase hydrogenation process, so that hydrogen is distributed in the oil product in micron-sized bubbles, thereby improving the mass transfer and heat transfer rate, reducing the severity and the operation cost of hydrogenation reaction.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a liquid phase hydrogenation strengthening hydrogen mixing device and method, which are used for improving the hydrogen dissolution amount and the gas-liquid mass transfer efficiency of hydrogen in the liquid phase hydrogenation process, and are particularly suitable for hydrogenation strengthening hydrogen mixing of synthetic oil.
Background
The trickle bed hydrogenation has the problems of large mass transfer resistance, large investment, high energy consumption and the like, thereby generating a liquid phase hydrogenation process, wherein the liquid phase is always a continuous phase in a reactor, hydrogen is a disperse phase, the reactor adopts a reactor with a structure similar to that of the trickle bed reactor, and the trickle bed hydrogenation process has the characteristics of low investment, low energy consumption, low running cost and the like due to the elimination of a circulating hydrogen system, but is only suitable for hydrogenation reactions with chemical hydrogen consumption of not more than 0.6wt% due to limited hydrogen dissolving capacity of an oil product, and limits the application of the liquid phase hydrogenation process in hydrogenation engineering such as high hydrogen consumption, inferior oil and the like.
At present, isoTherming technology, SRH technology and the like are mainly used for circularly dissolving hydrogen in the hydrogenated product, hydrogen required by the reaction is provided in an auxiliary way, a high-temperature and high-pressure circulating pump is required to be additionally arranged, and the investment cost and the potential safety hazard are increased. The China petrochemical CLTH technology and the C-NUM technology of China petroleum cancel a circulating oil system, simplify the process flow, reduce the investment and the operation cost, but the technology is only applied to a aviation kerosene liquid phase hydrogenation test with low hydrogen consumption, and can be used for hydrogenation of inferior oil products such as mixed diesel oil doped with catalytic diesel oil or coked diesel oil, FCC wax oil, residual oil and the like with higher hydrogen consumption or not to be further verified.
From the above analysis, if the liquid phase hydrogenation technology is to replace the application of gas phase trickle bed hydrogenation in high hydrogen consumption, the mixing effect of hydrogen in oil products needs to be enhanced by a static mixer or a dynamic mixer with a special structure, so that hydrogen bubbles reach a micron-sized ultrastable state, and the hydrogen dissolving amount in liquid is far more than the actual chemical hydrogen consumption.
CN109482131a discloses a gas-liquid reinforced mass transfer device based on porous ceramic membrane, which comprises a housing, wherein a plurality of membrane elements are arranged in the housing, two ends of the housing are respectively provided with a flower plate, the head of the housing is provided with a liquid inlet, the tail of the housing is provided with a gas-liquid outlet, and one side of the housing is provided with a gas inlet. The gas-liquid reinforced mass transfer device based on the porous ceramic membrane is simple to operate, low in maintenance requirement, good in gas-liquid mixing effect, low in coalescence degree, suitable for long-period operation, and capable of realizing efficient dispersion and mixing of gas-liquid two phases under lower energy consumption. The disadvantages of this technique or the shortcomings with respect to the present invention: the gas-liquid mixing mode of the device mainly depends on gas phase diffusion and laminar flow shear to strengthen gas-liquid mixing, so that the dissolved gas amount is small, and the bubbles are unevenly distributed.
CN102513040B relates to a microporous gas distributor, comprising a shell (1), wherein the shell (1) is provided with a gas inlet (5), a liquid inlet (6) and a liquid outlet (7); the shell (1) is internally provided with a ceramic membrane element (2), one end of the ceramic membrane element (2) is open, the other end is sealed by epoxy resin, and the air inlet (5) is communicated with the open end of the ceramic membrane element (2). The invention utilizes the micropore characteristic of the membrane material, gas enters from the open end of the ceramic membrane element and is discharged from micropores of the side wall, so that bubbles are tiny and uniform, liquid moves from the liquid inlet to the liquid outlet, bubbles diffused from the ceramic membrane element fully contact with the liquid in the shell, the gas-liquid mass transfer efficiency is improved, the ceramic membrane has the characteristics of high temperature resistance, high pressure, acid and alkali resistance and the like, can be used in various solutions for a long time, has long continuous operation time and stable operation, and reduces the operation cost. The technology has the defects that: because the ceramic element of the microporous gas distributor passes through the small holes on the partition plate, dead angles are easily formed between the ceramic element and the small holes, and when liquid flows in the shell, the liquid is easily blocked in the small holes to influence the outward diffusion of the gas in the ceramic element; thus, the device can only be used for gas-liquid mass transfer between a liquid and a gas which are low in viscosity and free of impurities, but is not suitable for hydrogenation of synthetic oils which are high in viscosity and contain a large amount of impurities.
CN102311790a discloses a liquid-phase cyclic hydrotreatment method for increasing the hydrogen mixing amount. The technological process of the invention is as follows: the liquid phase material (including fresh raw oil, circulating oil after reaction and circulating oil in the hypergravity hydrogen mixing equipment) and hydrogen enter the hypergravity hydrogen mixing equipment together, and the hydrogen is torn and divided into a large number of microbubbles through high-speed rotation of a gas-liquid mixing impeller, so that the gas-liquid mass transfer efficiency is greatly enhanced, the hydrogen is dissolved in the liquid phase material in a supersaturated state, and a large number of microbubbles are dispersed in the liquid phase material in an emulsified state and are brought into a reactor for hydrogenation reaction. The method adopts the hypergravity hydrogen mixing equipment, on one hand, greatly promotes the dissolution of hydrogen, and simultaneously removes gas phase impurities such as hydrogen sulfide, ammonia and the like more effectively, thereby promoting the reactions such as hydrodesulfurization, denitrification, aromatic hydrocarbon saturation, cracking and the like. The disadvantages of this technique or the shortcomings with respect to the present invention: although the invention can generate a large amount of micro bubbles and has good effect, the energy consumption is large in the operation process of the hypergravity equipment, the operation temperature and the operation pressure of the device are higher, the requirements on the material and the sealing performance of the equipment are higher, and the operation cost is high.
Therefore, the development of the liquid-phase hydrogenation enhanced hydrogen mixing process which has the advantages of simple system structure and long operation period, can be improved on the existing device, can adapt to the hydrofining or cracking of more high-hydrogen oil products, can reduce the operation cost and energy consumption of a hydrogenation device, can apply the transformation of an old device and the old property of a disc, and has the promotion effect on the quality improvement and the high-quality development of petroleum refining services.
Disclosure of Invention
The invention aims to provide a liquid-phase hydrogenation strengthening hydrogen mixing device and a method, which can improve the hydrogen dissolution amount of hydrogen in liquid-phase hydrogenation, and enable the hydrogen to exist in synthetic oil in the form of micro bubbles, thereby improving the mass transfer and heat transfer rate, and reducing the causticity scale and the operation cost of hydrogenation reaction. Meanwhile, the technical problems of high energy consumption and high operation cost of the liquid phase hydrogenation device in the prior art and uneven gas-liquid mixing of the strengthening gas-liquid mixing of the gas-liquid mixing mode depending on gas phase diffusion and laminar flow shearing are solved.
In order to achieve the above purpose, the liquid phase hydrogenation strengthening hydrogen mixing device comprises a shell and a porous ceramic membrane. One end of the shell is provided with a liquid inlet, the bottom is provided with an air inlet, the other end is provided with a gas-liquid mixing outlet; the porous ceramic membrane is arranged in the shell, openings at two ends of the porous ceramic membrane are respectively communicated with the liquid inlet and the gas-liquid mixing outlet, and the side wall of the porous ceramic membrane is communicated with the air inlet; the inside of porous ceramic membrane is equipped with a plurality of ceramic membrane baffles of crisscross placing from top to bottom.
In the liquid-phase hydrogenation strengthening hydrogen mixing device, preferably, the ceramic membrane baffle plate is provided with a hollow and communicated with the air inlet; the ceramic membrane baffle is semicircular; the material of the ceramic membrane baffle is the same as that of the porous ceramic membrane.
According to the liquid-phase hydrogenation strengthening hydrogen mixing device, the number of the porous ceramic membranes is multiple, and the porous ceramic membranes are longitudinally and parallelly arranged in the shell.
According to the liquid-phase hydrogenation strengthening hydrogen mixing device, the air inlet, the liquid inlet and the gas-liquid mixing outlet are separated by using sealing strips.
According to the liquid-phase hydrogenation strengthening hydrogen mixing device, the pore diameter of the porous ceramic membrane is 50-1000 nm, preferably 200-500 nm.
According to the liquid-phase hydrogenation strengthening hydrogen mixing device, the number of the ceramic membrane baffles is 20-250 per meter, the distance between two adjacent ceramic membrane baffles is 4-50 mm, the thickness of each ceramic membrane baffle is 1-10 mm, and the axial projection area of each ceramic membrane baffle is 50-80% of the cross section area of the porous ceramic membrane.
In the liquid-phase hydrogenation strengthening hydrogen mixing device, preferably, the number of the ceramic membrane baffles is 50-200 per meter, the distance between two adjacent ceramic membrane baffles is 5-20 mm, the thickness of each ceramic membrane baffle is 4-8 mm, and the axial projection area of each ceramic membrane baffle is 60-70% of the cross section area of the porous ceramic membrane.
The invention also provides a liquid phase hydrogenation strengthening hydrogen mixing method, which adopts the liquid phase hydrogenation strengthening hydrogen mixing device and comprises the following steps:
Synthetic oil enters the porous ceramic membrane from the liquid inlet of the shell, the synthetic oil forms turbulent flow under the action of the ceramic membrane baffle, hydrogen enters the shell through the air inlet, the pressure on one side of the hydrogen is slightly higher than that of the synthetic oil, the hydrogen permeates into the porous ceramic membrane through micropores under the action of pressure difference, a large number of microbubbles are produced by the hydrogen under the action of turbulent liquid shearing force, the hydrogen and the synthetic oil are mixed by the liquid-phase hydrogenation strengthening hydrogen mixing device to form a hydrogen-oil mixture in a microemulsion state, and the hydrogen-oil mixture leaves from the gas-liquid mixing outlet and enters the liquid-phase hydrogenation reactor for hydrogenation reaction.
According to the liquid phase hydrogenation strengthening hydrogen mixing method, the diameter of the micro bubbles is 200-900 mu m; the hydrogen dissolving amount of the hydrogen oil mixture is 2-4 times of the saturated hydrogen dissolving amount.
According to the liquid-phase hydrogenation enhanced hydrogen mixing method, the mode that the hydrogen oil mixture enters the liquid-phase hydrogenation reactor is that the hydrogen oil mixture is fed from the upper part of the liquid-phase hydrogenation reactor; the hydrogenation reaction has the following technological conditions: the reaction pressure is 1MPa to 15.0MPa, preferably 2MPa to 10.0MPa; the reaction temperature is 200-380 ℃, preferably 220-350 ℃; the hydrogen-oil ratio is 10:1-300:1, preferably 15:1-200:1; the volume space velocity is 0.1h -1～4.0h-1, preferably 0.2h -1～3.0h-1.
The invention can be further described as follows:
The synthetic oil and the hydrogen are mixed in the liquid-phase hydrogenation strengthening hydrogen mixing device with the baffle, the liquid-phase hydrogenation strengthening hydrogen mixing device with the baffle comprises a shell, a liquid inlet, an air inlet and a gas-liquid mixing outlet are formed in the shell, a plurality of porous ceramic membranes are arranged in the shell, two ends of each ceramic membrane are respectively provided with openings and are respectively communicated with the liquid inlet and the gas-liquid mixing outlet, the air inlet is communicated with the side wall of the ceramic membrane, and the air inlet is separated from (the liquid inlet and the gas-liquid mixing outlet) by using a sealing strip.
The porous ceramic membranes are longitudinally and parallelly arranged in the shell, and a plurality of microporous ceramic membrane semicircular baffles which are arranged in an up-down staggered mode are arranged in the ceramic membranes.
The semicircular baffle plate is provided with a hollow part which is communicated with the air inlet, and the baffle plate is made of the same material as the porous ceramic membrane.
The pore diameter of the porous ceramic membrane is 50 nm-1000 nm, preferably 200 nm-500 nm.
The number of the baffles is 20-250 per meter, preferably 50-200 per meter, the distance between two adjacent baffles is 4-50 mm, preferably 5-20 mm, the thickness of the baffles is 1-10 mm, preferably 4-8 mm, and the axial projection area of the baffles is 50-80% of the cross section area of the ceramic membrane, preferably 60-70%.
The working mode of the liquid phase hydrogenation strengthening hydrogen mixing device is as follows: oil enters a membrane tube of a ceramic membrane from a liquid inlet, liquid forms turbulent flow in the ceramic membrane due to the existence of a ceramic membrane baffle, the contact area between the liquid and hydrogen is increased, meanwhile, the hydrogen enters a shell from an air inlet, the pressure on one side of the gas is slightly higher than the pressure of the liquid, the hydrogen permeates into the ceramic membrane through micropores under the action of pressure difference, a large number of microbubbles are produced under the action of shearing force of turbulent liquid, experiments show that the hydrogen and the synthetic oil reach a micro-emulsion state after being mixed by a liquid-phase hydrogenation strengthening hydrogen mixing device, the particle size of the bubbles is reduced, the contact area of the gas and the liquid is increased, the diameter of the generated microbubbles is 200 mu m-900 mu m, the hydrogen dissolving amount of the synthetic oil is 2-4 times that of the saturated hydrogen dissolving amount, and then the hydrogen-oil mixture leaves from a gas-liquid outlet to enter a liquid-phase hydrogenation reactor.
The hydrogen oil mixture is fed from the upper part of the hydrogenation reactor, a cylindrical or clover-shaped hydrofining catalyst is placed in the hydrogenation reactor, and the synthetic oil with excessive saturated hydrogen is contacted with the catalyst to react, so that no additional hydrogen supplement is needed in the reaction process. The hydrogenation reaction process conditions are that the reaction pressure is 1 MPa-15.0 MPa, preferably 2 MPa-10.0 MPa, the reaction temperature is 200-380 ℃, preferably 220-350 ℃, the hydrogen-oil ratio is 10:1-300:1, preferably 15:1-200:1, and the volume airspeed is 0.1h -1～4.0h-1, preferably 0.2h -1～3.0h-1.
The liquid-phase hydrogenation strengthening hydrogen mixing device with the baffle plate has the main effects that hydrogen is dissolved in synthetic oil in micron-sized bubbles, so that the hydrogen is in a supersaturated state in the oil, the gas-liquid mass transfer rate and the hydrogenation effect can be obviously increased when hydrogenation reaction is carried out, and the reaction severity is effectively reduced. Compared with the prior art, the invention has the following advantages:
The liquid phase hydrogenation strengthening hydrogen mixing device is internally provided with a plurality of baffles, under the action of the baffles, fluid is changed into turbulent flow from laminar flow, the fluid flow is more turbulent, the contact opportunity between the inside of the fluid and the inner wall of the ceramic membrane is increased, hydrogen bubbles and the liquid are more fully mixed, and meanwhile, the contact area between the liquid and the hydrogen bubbles can be increased by the microporous ceramic membrane baffles, so that the hydrogen dissolving amount of an oil product is remarkably improved, and the hydrogen dissolving amount of the oil product can reach 2-4 times of saturated hydrogen dissolving. In addition, a plurality of ceramic membrane baffles which are arranged in the porous ceramic membrane and are staggered up and down can avoid the accumulation and blockage of synthetic oil.
When the liquid phase hydrogenation enhanced hydrogen mixing method is used for hydrogenation reaction, oil circulation is not needed, additional hydrogen supplementing is not needed, the method can reduce the operating pressure, temperature or hydrogen-oil ratio of the existing hydrogenation device, and can greatly reduce the investment cost and the operation cost. Meanwhile, compared with the prior art, the device is simple to operate, low in bubble coalescence degree, acid-resistant, alkali-resistant and high-temperature-resistant in ceramic membrane, suitable for mixing hydrogen with various oil products, capable of guaranteeing long-period stable operation of the device, low in operation cost and wide in application prospect.
Drawings
FIG. 1 is a schematic diagram of a liquid phase hydrogenation enhanced hydrogen mixing apparatus according to an embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of an embodiment of a liquid phase hydrogenation enhanced hydrogen mixing device according to the present invention.
FIG. 3 is a schematic longitudinal section of an embodiment of a liquid-phase hydrogenation enhanced hydrogen mixing device according to the present invention.
FIG. 4 is a schematic flow chart of an embodiment of the liquid phase hydrogenation enhanced hydrogen mixing process of the present invention.
Wherein, the reference numerals:
1. Shell body
2. Liquid inlet
3. Air inlet
4. Gas-liquid mixing outlet
5. Porous ceramic membrane
6. Semicircular baffle plate for ceramic membrane
7. Hollowed-out part
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Raw material or equipment source: raw materials: synthetic oil PAO40, device: 200ML liquid phase hydrogenation evaluation device
Evaluation analysis method:
In order to improve the hydrogen dissolution amount of hydrogen in liquid phase hydrogenation, solve the technical problems of uneven gas-liquid mixing and small hydrogen dissolution amount caused by gas phase diffusion and laminar flow shearing in the gas-liquid mixing mode in the prior art, improve the gas-liquid mass transfer efficiency and the reaction effect in the liquid phase hydrogenation process, and reduce the reaction severity, the invention provides a liquid phase hydrogenation reinforced hydrogen mixing device and a liquid phase hydrogenation reinforced hydrogen mixing method.
FIG. 1 is a schematic diagram of a liquid phase hydrogenation enhanced hydrogen mixing apparatus according to an embodiment of the present invention. The liquid phase hydrogenation strengthening hydrogen mixing device comprises a shell 1 and a porous ceramic membrane 5, wherein one end of the shell 1 is provided with a liquid inlet 2, the other end of the shell is provided with a gas-liquid mixing outlet 4, the bottom of the shell is provided with an air inlet 3, a plurality of porous ceramic membranes 5 are arranged in the shell 1, two ends of each porous ceramic membrane 5 are open and are respectively communicated with the liquid inlet 2 and the gas-liquid mixing outlet 4, the air inlet 3 is communicated with the side wall of the porous ceramic membrane 5, and the air inlet 3 is separated from (the liquid inlet 2 and the gas-liquid mixing outlet 4) by using sealing strips. A plurality of ceramic membrane baffles 6 which are arranged in a staggered way up and down are arranged inside the porous ceramic membrane 5.
Preferably, the number of the porous ceramic membranes 5 is set to be plural, and the plural porous ceramic membranes 5 are arranged in parallel in the longitudinal direction within the housing 1. The pore diameter of the porous ceramic membrane 5 is 50nm to 1000nm, preferably 200nm to 500nm.
The ceramic membrane baffle 6 is provided with a hollow 7 communicated with the air inlet 3. The shape of the ceramic membrane baffle 6 is semicircular, and the material of the ceramic membrane baffle 6 is the same as that of the porous ceramic membrane 5. The number of the ceramic membrane baffles 6 is 20-250 per meter, preferably 50-200 per meter; the distance between two adjacent ceramic membrane baffles 6 is 4 mm-50 mm, preferably, the distance between two adjacent ceramic membrane baffles 6 is 5 mm-20 mm; the thickness of the ceramic membrane baffle 6 is 1mm to 10mm, preferably, the thickness of the ceramic membrane baffle 6 is 4mm to 8mm; the axial projection area of the ceramic membrane baffle 6 is 50% -80% of the cross-sectional area of the porous ceramic membrane 5, and preferably, the axial projection area of the ceramic membrane baffle 6 is 60% -70% of the cross-sectional area of the porous ceramic membrane 5.
The liquid phase hydrogenation strengthening hydrogen mixing method provided by the invention comprises the following steps: : synthetic oil enters a membrane tube of a porous ceramic membrane 5 from a liquid inlet 2 of a shell 1, the synthetic oil forms turbulent flow under the action of a ceramic membrane baffle 6, hydrogen enters the shell 1 through an air inlet 3, the pressure on one side of the gas is slightly larger than the liquid pressure, the hydrogen permeates into the porous ceramic membrane 5 through micropores under the action of pressure difference, a large number of microbubbles are produced by the hydrogen under the action of turbulent liquid shearing force, the hydrogen and the synthetic oil are mixed by a liquid-phase hydrogenation strengthening hydrogen mixing device to form a hydrogen-oil mixture in a microemulsion state, and then the hydrogen-oil mixture leaves from a gas-liquid mixing outlet 4 and enters a liquid-phase hydrogenation reactor for hydrogenation reaction.
FIG. 4 is a schematic flow chart of an embodiment of the liquid phase hydrogenation enhanced hydrogen mixing process of the present invention. The mode that the hydrogen oil mixture enters the hydrogenation reactor is that the mixture is fed from the upper part of the hydrogenation reactor, a cylindrical or clover-shaped hydrofining catalyst is placed in the hydrogenation reactor, the synthetic oil with excessive saturated hydrogen is contacted with the catalyst to react, and the reaction process does not need additional hydrogen supplementing. The hydrogenation reaction process conditions are as follows: the reaction pressure is 1MPa to 15.0MPa, preferably 2MPa to 10.0MPa; the reaction temperature is 200-380 ℃, preferably 220-350 ℃; the hydrogen-oil ratio is 10:1-300:1, preferably 15:1-200:1; the volume space velocity is 0.1h -1～4.0h-1, preferably 0.2h -1～3.0h-1.
The liquid-phase hydrogenation strengthening hydrogen mixing device with the baffle plate has the main effects that synthetic oil and hydrogen are mixed in a mixer based on a porous ceramic membrane, the hydrogen is dissolved in the synthetic oil in the form of bubbles with the diameter of 200-900 mu m by using turbulent flow of the liquid and shearing action of the bubbles, so that the hydrogen in the oil is in a supersaturated state, the hydrogen dissolution amount of the synthetic oil is 2-4 times of the saturated hydrogen dissolution amount, the mass transfer rate of the gas and the liquid and the hydrogenation effect can be obviously increased when hydrogenation reaction is carried out, and the reaction severity is effectively reduced.
Example 1
In the liquid-phase hydrogenation strengthening hydrogen mixing device of the embodiment, the number of the porous ceramic membranes is 12, the porous ceramic membranes are longitudinally and parallelly arranged in the shell, the average pore diameter of the porous ceramic membranes is 400nm, the number of the ceramic membrane baffles is 100 per meter, the distance between two adjacent ceramic membrane baffles is 10mm, the thickness of the ceramic membrane baffles is 3mm, and the axial projection area of the ceramic membrane baffles is 60% of the cross section area of the porous ceramic membranes. The synthetic oil PAO40 and hydrogen are mixed by a liquid phase hydrogenation strengthening hydrogen mixing device to produce a large number of micro bubbles under the action of turbulent liquid shearing force, the diameter of the micro bubbles is 300-700 mu m, and the hydrogen dissolving amount of the mixed hydrogen oil mixture is 3-4 times of the saturated hydrogen dissolving amount. The hydrogen oil mixture is heated and then directly enters a hydrogenation reactor from the top for hydrogenation reaction, the hydrogenation reactor comprises a catalyst bed layer, the obtained product is refined PAO40, and the hydrogenation process conditions are as follows: the reaction pressure is 4.0MPa, the reaction temperature is 265 ℃, the volume space velocity is 0.2h -1, and the hydrogen-oil ratio is 40:1; the raw material properties and the product properties are shown in Table 1.
Comparative example 1
The synthetic oil PAO40 and hydrogen are directly fed into a hydrogenation reactor from the top after being heated without a liquid phase hydrogenation strengthening hydrogen mixing device for conventional liquid phase hydrogenation, hydrogenation reaction is carried out, the hydrogenation reactor comprises a catalyst bed layer, the obtained product is refined PAO40, and the hydrogenation process conditions are as follows: the reaction pressure is 4.0MPa, the reaction temperature is 265 ℃, the volume space velocity is 0.2h -1, and the hydrogen-oil ratio is 40:1; the product properties are shown in Table 1.
Example 2
In the liquid-phase hydrogenation strengthening hydrogen mixing device of the embodiment, the number of the porous ceramic membranes is 12, the porous ceramic membranes are longitudinally and parallelly arranged in the shell, the average pore diameter of the porous ceramic membranes is 1000nm, the number of the ceramic membrane baffles is 20 per meter, the distance between two adjacent ceramic membrane baffles is 50mm, the thickness of the ceramic membrane baffles is 10mm, and the axial projection area of the ceramic membrane baffles is 80% of the cross section area of the porous ceramic membranes. The synthetic oil PAO40 and hydrogen are mixed by a liquid phase hydrogenation strengthening hydrogen mixing device to produce a large number of micro bubbles under the action of turbulent liquid shearing force, the diameter of the micro bubbles is 500-900 mu m, and the hydrogen dissolving amount of the mixed hydrogen oil mixture is 2-3 times of the saturated hydrogen dissolving amount. The hydrogen oil mixture is heated and then directly enters a hydrogenation reactor from the top for hydrogenation reaction, the hydrogenation reactor comprises a catalyst bed layer, the obtained product is refined PAO40, and the hydrogenation process conditions are as follows: the reaction pressure is 3.0MPa, the reaction temperature is 265 ℃, the volume space velocity is 0.2h -1, and the hydrogen-oil ratio is 40:1; the product properties are shown in Table 1.
Example 3
In the liquid-phase hydrogenation strengthening hydrogen mixing device of the embodiment, the number of the porous ceramic membranes is 12, the porous ceramic membranes are longitudinally and parallelly arranged in the shell, the average pore diameter of the porous ceramic membranes is 50nm, the number of the ceramic membrane baffles is 250 per meter, the distance between two adjacent ceramic membrane baffles is 4mm, the thickness of the ceramic membrane baffles is 1mm, and the axial projection area of the ceramic membrane baffles is 50% of the cross section area of the porous ceramic membranes. The synthetic oil PAO40 and hydrogen are mixed by a liquid phase hydrogenation strengthening hydrogen mixing device to produce a large number of micro bubbles under the action of turbulent liquid shearing force, the diameter of the micro bubbles is 200-600 mu m, and the hydrogen dissolving amount of the mixed hydrogen oil mixture is 3-4 times of the saturated hydrogen dissolving amount. The hydrogen oil mixture is heated and then directly enters a hydrogenation reactor from the top for hydrogenation reaction, the hydrogenation reactor comprises a catalyst bed layer, the obtained product is refined PAO40, and the hydrogenation process conditions are as follows: the reaction pressure is 4.0MPa, the reaction temperature is 255 ℃, the volume space velocity is 0.2h -1, and the hydrogen-oil ratio is 40:1; the product properties are shown in Table 1.
Example 4
In the liquid-phase hydrogenation strengthening hydrogen mixing device of the embodiment, the number of the porous ceramic membranes is 12, the porous ceramic membranes are longitudinally and parallelly arranged in the shell, the average pore diameter of the porous ceramic membranes is 200nm, the number of the ceramic membrane baffles is 200 per meter, the distance between two adjacent ceramic membrane baffles is 5mm, the thickness of the ceramic membrane baffles is 2mm, and the axial projection area of the ceramic membrane baffles is 70% of the cross section area of the porous ceramic membranes. The synthetic oil PAO40 and hydrogen are mixed by a liquid phase hydrogenation strengthening hydrogen mixing device to produce a large number of micro bubbles under the action of turbulent liquid shearing force, the diameter of the micro bubbles is 400-800 mu m, and the hydrogen dissolving amount of the mixed hydrogen oil mixture is 3-4 times of the saturated hydrogen dissolving amount. The hydrogen oil mixture is heated and then directly enters a hydrogenation reactor from the top for hydrogenation reaction, the hydrogenation reactor comprises a catalyst bed layer, the obtained product is refined PAO40, and the hydrogenation process conditions are as follows: the reaction pressure is 4.0MPa, the reaction temperature is 265 ℃, the volume space velocity is 0.4h -1, and the hydrogen-oil ratio is 40:1; the product properties are shown in Table 1.
Example 5
In the liquid-phase hydrogenation strengthening hydrogen mixing device of the embodiment, the number of the porous ceramic membranes is 12, the porous ceramic membranes are longitudinally and parallelly arranged in the shell, the average pore diameter of the porous ceramic membranes is 800nm, the number of the ceramic membrane baffles is 100 per meter, the distance between two adjacent ceramic membrane baffles is 10mm, the thickness of the ceramic membrane baffles is 3mm, and the axial projection area of the ceramic membrane baffles is 60% of the cross section area of the porous ceramic membranes. The synthetic oil PAO40 and hydrogen are mixed by a liquid phase hydrogenation strengthening hydrogen mixing device to produce a large number of micro bubbles under the action of turbulent liquid shearing force, the diameter of the micro bubbles is 400-900 mu m, and the hydrogen dissolving amount of the mixed hydrogen oil mixture is 2-3 times of the saturated hydrogen dissolving amount. The hydrogen oil mixture is heated and then directly enters a hydrogenation reactor from the top for hydrogenation reaction, the hydrogenation reactor comprises a catalyst bed layer, the obtained product is refined PAO40, and the hydrogenation process conditions are as follows: the reaction pressure is 4.0MPa, the reaction temperature is 265 ℃, the volume space velocity is 0.2h -1, and the hydrogen-oil ratio is 20:1; the product properties are shown in Table 1.
Table 1 raw material and product properties of examples and comparative examples
As can be seen from the data obtained in the examples and the comparative examples, under the same process conditions, compared with the conventional liquid-phase hydrotreatment PAO40, the enhanced hydrogen mixing device and the method have the advantages that the bromine number, the aromatic hydrocarbon content and the Sibo characteristic number are all improved, and meanwhile, under the condition that various indexes of target products are basically equivalent, the reaction pressure of the process method can be reduced by 1.0MPa or the reaction temperature can be reduced by 10 ℃ or the airspeed can be improved by 2 times or the hydrogen can be saved by 50% compared with the existing liquid-phase hydrogenation process method, and the severity of the reaction conditions in the subsequent hydrogenation reaction process can be obviously reduced by the synthetic oil and the hydrogen mixed by the liquid-phase enhanced hydrogen mixing device and the method.
Claims (10)
1. A liquid phase hydrogenation enhanced hydrogen mixing device for synthetic oil, comprising:
One end of the shell is provided with a liquid inlet, the bottom is provided with an air inlet, the other end is provided with a gas-liquid mixing outlet; the porous ceramic membrane is arranged in the shell, openings at two ends of the porous ceramic membrane are respectively communicated with the liquid inlet and the gas-liquid mixing outlet, and the side wall of the porous ceramic membrane is communicated with the air inlet;
A plurality of ceramic membrane baffles which are arranged in a staggered manner up and down are arranged in the porous ceramic membrane; the ceramic membrane baffle is provided with a hollow and communicated with the air inlet; the ceramic membrane baffles are semicircular, the number of the ceramic membrane baffles is 20-250 per meter, the distance between two adjacent ceramic membrane baffles is 4-50 mm, the thickness of each ceramic membrane baffle is 1-10 mm, and the axial projection area of each ceramic membrane baffle is 50-80% of the cross section area of the porous ceramic membrane;
the pore diameter of the porous ceramic membrane is 50 nm-1000 nm.
2. The liquid-phase hydrogenation enhanced hydrogen mixing device for synthetic oil according to claim 1, wherein the material of the ceramic membrane baffle is the same as the material of the porous ceramic membrane.
3. The liquid-phase hydrogenation enhanced hydrogen mixing device for synthetic oil according to claim 1, wherein the number of said porous ceramic membranes is plural, and a plurality of said porous ceramic membranes are arranged in parallel in the longitudinal direction in said housing.
4. The liquid-phase hydrogenation enhanced hydrogen mixing device for synthetic oil according to claim 1, wherein the gas inlet is separated from the liquid inlet and the gas-liquid mixing outlet by using sealing strips.
5. The liquid-phase hydrogenation enhanced hydrogen mixing device for synthetic oil according to claim 1, wherein the pore diameter of the porous ceramic membrane is 200 nm-500 nm.
6. The liquid-phase hydrogenation reinforced hydrogen mixing device for synthetic oil according to claim 1, wherein the number of the ceramic membrane baffles is 50-200 per meter, the distance between two adjacent ceramic membrane baffles is 5 mm-20 mm, the thickness of each ceramic membrane baffle is 4 mm-8 mm, and the axial projection area of each ceramic membrane baffle is 60% -70% of the cross-sectional area of the porous ceramic membrane.
7. A liquid phase hydrogenation enhanced hydrogen mixing method, adopting the liquid phase hydrogenation enhanced hydrogen mixing device for synthetic oil according to any one of claims 1 to 6, characterized by comprising the following steps:
Synthetic oil enters the porous ceramic membrane from the liquid inlet of the shell, the synthetic oil forms turbulent flow under the action of the ceramic membrane baffle, hydrogen enters the shell through the air inlet, the pressure on one side of the hydrogen is slightly higher than that of the synthetic oil, the hydrogen permeates into the porous ceramic membrane through micropores under the action of pressure difference, a large number of microbubbles are produced by the hydrogen under the action of turbulent liquid shearing force, the hydrogen and the synthetic oil are mixed by the liquid-phase hydrogenation strengthening hydrogen mixing device to form a hydrogen-oil mixture in a microemulsion state, and the hydrogen-oil mixture leaves from the gas-liquid mixing outlet and enters the liquid-phase hydrogenation reactor for hydrogenation reaction.
8. The liquid phase hydrogenation enhanced hydrogen mixing method according to claim 7, wherein the diameter of the micro bubbles is 200 μm to 900 μm; the hydrogen dissolution amount of the hydrogen oil mixture is 2-4 times of the saturated hydrogen dissolution amount.
9. The liquid phase hydrogenation enhanced hydrogen mixing method according to claim 7, wherein the hydrogen oil mixture enters the liquid phase hydrogenation reactor in a manner of feeding from the upper part of the liquid phase hydrogenation reactor; the hydrogenation reaction has the following technological conditions: the reaction pressure is 1MPa to 15.0MPa; the reaction temperature is 200-380 ℃; the hydrogen-oil ratio is 10:1-300:1; the volume space velocity was 0.1h -1～4.0h-1.
10. The liquid phase hydrogenation enhanced hydrogen mixing method according to claim 9, wherein the process conditions of the hydrogenation reaction are: the reaction pressure is 2MPa to 10.0MPa; the reaction temperature is 220-350 ℃; the hydrogen-oil ratio is 15:1-200:1; the volume space velocity was 0.2h -1～3.0h-1.
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| CN202376975U (en) * | 2011-12-29 | 2012-08-15 | 江苏久吾高科技股份有限公司 | Ceramic membrane micropore air distributor |
| CN109482131A (en) * | 2017-09-12 | 2019-03-19 | 江苏赛瑞迈科新材料有限公司 | Gas-liquid reinforcing mass transfer device based on porous ceramic film |
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| CN110877294B (en) * | 2019-12-06 | 2020-11-10 | 南京尚吉增材制造研究院有限公司 | High-negative-pressure micro-nano bubble enhanced abrasive flow cavitation polishing device and method |
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| CN102513040A (en) * | 2011-12-29 | 2012-06-27 | 江苏久吾高科技股份有限公司 | Microporous gas distributor of ceramic membrane |
| CN202376975U (en) * | 2011-12-29 | 2012-08-15 | 江苏久吾高科技股份有限公司 | Ceramic membrane micropore air distributor |
| CN109482131A (en) * | 2017-09-12 | 2019-03-19 | 江苏赛瑞迈科新材料有限公司 | Gas-liquid reinforcing mass transfer device based on porous ceramic film |
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