CN115404100A - Hydrogenation device and hydrogenation method for coupling fluidized bed and fixed bed - Google Patents
Hydrogenation device and hydrogenation method for coupling fluidized bed and fixed bed Download PDFInfo
- Publication number
- CN115404100A CN115404100A CN202211190879.1A CN202211190879A CN115404100A CN 115404100 A CN115404100 A CN 115404100A CN 202211190879 A CN202211190879 A CN 202211190879A CN 115404100 A CN115404100 A CN 115404100A
- Authority
- CN
- China
- Prior art keywords
- gas
- oil
- reaction
- hydrogen
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000008878 coupling Effects 0.000 title abstract description 3
- 238000010168 coupling process Methods 0.000 title abstract description 3
- 238000005859 coupling reaction Methods 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 238000009835 boiling Methods 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 233
- 239000003921 oil Substances 0.000 claims description 220
- 239000007788 liquid Substances 0.000 claims description 206
- 238000000926 separation method Methods 0.000 claims description 203
- 239000007789 gas Substances 0.000 claims description 145
- 239000001257 hydrogen Substances 0.000 claims description 141
- 229910052739 hydrogen Inorganic materials 0.000 claims description 141
- 239000000047 product Substances 0.000 claims description 128
- 229930195733 hydrocarbon Natural products 0.000 claims description 97
- 150000002430 hydrocarbons Chemical class 0.000 claims description 97
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 96
- 239000004215 Carbon black (E152) Substances 0.000 claims description 94
- 239000011265 semifinished product Substances 0.000 claims description 91
- 239000007791 liquid phase Substances 0.000 claims description 79
- 239000000295 fuel oil Substances 0.000 claims description 65
- 230000001174 ascending effect Effects 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 229910001868 water Inorganic materials 0.000 claims description 46
- 150000002431 hydrogen Chemical class 0.000 claims description 45
- 238000002955 isolation Methods 0.000 claims description 43
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- 239000013589 supplement Substances 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 27
- 238000007789 sealing Methods 0.000 claims description 27
- 239000003225 biodiesel Substances 0.000 claims description 25
- 238000011144 upstream manufacturing Methods 0.000 claims description 15
- 239000002737 fuel gas Substances 0.000 claims description 10
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000000571 coke Substances 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 134
- 238000010586 diagram Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000010806 kitchen waste Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Images
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of hydrogenation, in particular to a hydrogenation device and a hydrogenation method for coupling a fluidized bed and a fixed bed. The hydrogenation device and the hydrogenation method solve the problems that a fixed bed catalyst bed layer is easy to coke and block, a fixed bed catalyst is easy to pulverize, a conventional boiling bed cannot completely hydrodeoxygenate and remove impurities from raw materials, and the combined investment of the conventional boiling bed and the fixed bed is large.
Description
Technical Field
The invention relates to the technical field of hydrogenation, in particular to a hydrogenation device and a hydrogenation method with coupled fluidized bed and fixed bed.
Background
The second-generation biodiesel is a renewable biomass fuel produced by taking non-edible animal and vegetable oil such as palm rancid oil, acidified oil, kitchen waste oil and the like as raw materials and adopting a hydrogenation method, and compared with mineral diesel, the renewable biomass fuel has the characteristics of renewability, excellent biodegradability, low sulfur content, low pollutant emission and the like, is real green diesel, and can become an ideal alternative energy source of petroleum fuel.
Researches show that the rancid palm oil, acidified oil, kitchen waste oil and the like contain a large amount of metal ions and high impurity content, and due to the characteristics of the special properties of the oil, such as high conductivity, high oxygen content, poor thermal stability, high boiling point and the like, conventional demetallization methods, such as an electric desalting method, a distillation method and the like cannot be implemented, if the electric desalting process easily causes electrode breakdown, the distillation easily causes condensation and cracking of fatty acid in the oil, and more inconvenience is brought to subsequent processing; because the grease has high viscosity, the filter is easy to block in the process of filtering impurities by adopting the filter with high precision, and only coarse filtration can be adopted, so most of metal and impurities in the grease can be brought into a subsequent reaction system.
The conventional hydrogenation method has the following problems: 1. by adopting the conventional fixed bed for hydrogenation, metals and impurities are easy to cause coking and blockage of a catalyst bed layer, and the operation period is seriously shortened; 2. the conventional fixed bed hydrogenation is adopted, so that the high oxygen content easily causes pulverization and inactivation of the fixed bed catalyst, and the cost of the catalyst is greatly increased; 3. the conventional fluidized bed or suspension bed hydrogenation is adopted, so that the deoxidation is not thorough, and qualified biodiesel cannot be produced; 4. the method of pre-deoxidizing by using a suspension bed or a boiling bed and then deeply hydrogenating by using a fixed bed needs to be provided with two sets of high-pressure hydrogenation systems, so that the investment of the device is greatly increased.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a hydrogenation device and a hydrogenation method which are coupled by an ebullated bed and a fixed bed.
The purpose of the invention is realized by the following technical scheme: a hydrogenation device with coupled boiling bed and fixed bed comprises a heavy oil rectifying tower, a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, a gas-liquid separation region, an uplink reaction region and a downlink reaction region are sequentially arranged in the reactor shell from top to bottom, an upper sealing disc is arranged between the top isolation region and the gas-liquid separation region, an interception grid is arranged between the gas-liquid separation region and the uplink reaction region, a lower sealing disc is arranged between the uplink reaction region and the downlink reaction region, at least one fluidized bed catalyst bed layer is arranged in the uplink reaction region, at least one fixed bed catalyst bed layer is arranged in the downlink reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the uplink reaction region, and a communicating pipe is arranged between the top of the gas-liquid separation region and the top of the downlink reaction region; the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with a semi-finished product inlet and at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
a raw oil conveying pipeline is connected to the main feeding inlet, a liquid phase outlet is connected with the heavy oil rectifying tower, a pressure reducing valve is arranged between the liquid phase outlet and the heavy oil rectifying tower, a semi-finished product conveying pipeline and a tail oil conveying pipeline are respectively connected to two liquid phase outlets of the heavy oil rectifying tower, the semi-finished product conveying pipeline is connected with the semi-finished product inlet, and the middle part of the tail oil conveying pipeline is connected with the raw oil conveying pipeline;
the main product outlet is connected with the inlet of the cold high-pressure separator, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplement inlet, the second hydrogen supplement inlet and the raw oil conveying pipeline.
A hydrogenation method of a hydrogenation device with coupled ebullated bed and fixed bed comprises the following steps:
(1) Raw oil enters a top isolation region from a main feeding inlet and is then conveyed to the bottom of an upper reaction region through a downcomer;
(2) In the upstream reaction zone, raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the hydrogen/oil volume ratio is 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe, and the heavy oil is depressurized by a depressurization valve and then conveyed to a heavy oil separation part;
(4) In the heavy oil separation part, the heavy oil is rectified to separate a semi-finished product, tail oil, non-condensable gas and water; at least one part of semi-finished products are sent to a descending reaction zone, at least one part of tail oil returns to an ascending reaction zone through a main feeding inlet, and the rest part of tail oil is discharged outside;
(5) In the downstream reaction zone, hot oil gas from the gas-liquid separation zone and a semi-finished product from the heavy oil separation part complete hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(6) In the cold high-pressure separation part, the product of the fixed bed hydrogenation reaction is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(7) In the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
The purpose of the invention is realized by the following technical scheme: a hydrogenation device with coupled boiling bed and fixed bed comprises a heavy oil rectifying tower, a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, an uplink reaction region, a gas-liquid separation region and a downlink reaction region are sequentially arranged in the reactor shell from top to bottom, an upper sealing disc is arranged between the top isolation region and the uplink reaction region, a middle sealing disc is arranged between the uplink reaction region and the gas-liquid separation region, a lower sealing disc is arranged between the gas-liquid separation region and the downlink reaction region, at least one fluidized bed catalyst bed layer is arranged in the uplink reaction region, at least one fixed bed catalyst bed layer is arranged in the downlink reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the uplink reaction region, a communicating pipe is arranged between the gas-liquid separation region and the top of the downlink reaction region, and a collecting pipe is arranged between the top of the gas-liquid separation region and the top of the gas-liquid separation region; the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with a semi-finished product inlet and at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the liquid phase outlet is connected with a heavy oil rectifying tower, a pressure reducing valve is arranged between the liquid phase outlet and the heavy oil rectifying tower, two liquid phase outlets of the heavy oil rectifying tower are respectively connected with a semi-finished product conveying pipeline and a tail oil conveying pipeline, the semi-finished product conveying pipeline is connected with the semi-finished product inlet, and the middle part of the tail oil conveying pipeline is connected with the raw oil conveying pipeline;
the main product outlet is connected with the inlet of the cold high-pressure separator, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplement inlet, the second hydrogen supplement inlet and the raw oil conveying pipeline.
A hydrogenation method of a hydrogenation device with coupled ebullated bed and fixed bed comprises the following steps:
(1) Raw oil enters a top isolation region from a main feeding inlet and is then conveyed to the bottom of an upper reaction region through a downcomer;
(2) In the upstream reaction zone, raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst at a temperature of 200-500 ℃, a pressure of 3.0-25.0 MPa and a hydrogen/oil volume ratio of 50-2000, so as to generate an ebullated bed product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon, and the ebullated bed product flows downwards to a gas-liquid separation zone through a collecting pipe;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe, and the heavy oil is depressurized by a depressurization valve and then conveyed to a heavy oil separation part;
(4) In the heavy oil separation part, the heavy oil is rectified to separate a semi-finished product, tail oil, non-condensable gas and water; at least one part of semi-finished products are sent to a descending reaction zone, at least one part of tail oil returns to an ascending reaction zone through a main feeding inlet, and the rest part of tail oil is discharged outside;
(5) In the downstream reaction zone, hot oil gas from the gas-liquid separation zone and a semi-finished product from the heavy oil separation part complete hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, so as to generate a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon;
(6) In the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(7) In the product separation part, the cold high-fraction oil liquid is subjected to a rectification process to separate gas, a biological light oil product and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are sent out as products.
The purpose of the invention is realized by the following technical scheme: a hydrogenation device with coupled boiling bed and fixed bed comprises a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, a gas-liquid separation region, an uplink reaction region and a downlink reaction region are sequentially arranged in the reactor shell from top to bottom, an upper sealing disc is arranged between the top isolation region and the gas-liquid separation region, an interception grid is arranged between the gas-liquid separation region and the uplink reaction region, a lower sealing disc is arranged between the uplink reaction region and the downlink reaction region, at least one fluidized bed catalyst bed layer is arranged in the uplink reaction region, at least one fixed bed catalyst bed layer is arranged in the downlink reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the uplink reaction region, and a communicating pipe is arranged between the top of the gas-liquid separation region and the top of the downlink reaction region; the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the inlet of the cold high-pressure separator is respectively connected with the liquid phase outlet and the main product outlet, a stop valve is arranged between the inlet of the cold high-pressure separator and the liquid phase outlet, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplementing inlet, the second hydrogen supplementing inlet and the raw oil conveying pipeline.
A hydrogenation method of a hydrogenation device with coupled ebullated bed and fixed bed comprises the following steps:
(1) When the raw oil is inferior raw oil, the inferior raw oil enters the top isolation region from the main feeding inlet and is then conveyed to the bottom of the upward reaction region through the downcomer;
(2) In the upstream reaction zone, the inferior raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions of a temperature of 200-500 ℃, a pressure of 3.0-25.0 MPa and a hydrogen/oil volume ratio of 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, and the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe;
(4) In the downstream reaction zone, the hot oil gas from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) In the cold high-pressure separation part, the fixed bed hydrogenation reaction product and the heavy oil from the gas-liquid separation zone are cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) In the product separation part, the cold high-oil separation liquid is subjected to a rectification process to remove non-condensable gas to obtain a semi-finished product, and the semi-finished product is filtered to remove impurities and then is sent to a semi-finished product storage tank.
Preferably, the method further comprises the following steps:
(1) when the raw oil is a semi-finished product, firstly closing a stop valve on a liquid phase outlet pipeline of the gas-liquid separation zone, enabling the filtered and impurity-removed semi-finished product to enter a top separation zone from a feeding inlet, and then conveying the semi-finished product to the bottom of an upper reaction zone through a downcomer;
(2) in the upstream reaction zone, the semi-finished product completes the pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the volume ratio of hydrogen to oil is 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon;
(3) gas-liquid separation is not carried out in the gas-liquid separation zone, and the product of the fluidized bed directly flows downwards to the top of the descending reaction zone through the communicating pipe;
(4) in the downstream reaction zone, the fluidized bed product from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) in the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) in the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
The purpose of the invention is realized by the following technical scheme: a hydrogenation device with coupled boiling bed and fixed bed comprises a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, an ascending reaction region, a gas-liquid separation region and a descending reaction region are sequentially arranged in the reactor shell from top to bottom, an upper sealing disc is arranged between the top isolation region and the ascending reaction region, a middle sealing disc is arranged between the ascending reaction region and the gas-liquid separation region, a lower sealing disc is arranged between the gas-liquid separation region and the descending reaction region, at least one fluidized bed catalyst bed layer is arranged in the ascending reaction region, at least one fixed bed catalyst bed layer is arranged in the descending reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the ascending reaction region, a communicating pipe is arranged between the top of the gas-liquid separation region and the top of the gas-liquid separation region;
the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the inlet of the cold high-pressure separator is respectively connected with the liquid phase outlet and the main product outlet, a stop valve is arranged between the inlet of the cold high-pressure separator and the liquid phase outlet, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplementing inlet, the second hydrogen supplementing inlet and the raw oil conveying pipeline.
A hydrogenation method of a hydrogenation device with coupled ebullated bed and fixed bed comprises the following steps:
(1) When the raw oil is inferior raw oil, the inferior raw oil enters the top isolation region from the main feeding inlet and is then conveyed to the bottom of the upward reaction region through the downcomer;
(2) In the upstream reaction zone, the poor-quality raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the hydrogen/oil volume ratio is 50-2000, so as to generate an ebullated bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon, and the ebullated bed product flows downwards to a gas-liquid separation zone through a collecting pipe;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, and the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe;
(4) In the downstream reaction zone, the hot oil gas from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) In the cold high-pressure separation part, the fixed bed hydrogenation reaction product and the heavy oil from the gas-liquid separation zone are cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least a part of cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) In the product separation part, the cold high-oil separation liquid is subjected to a rectification process to remove non-condensable gas to obtain a semi-finished product, and the semi-finished product is filtered to remove impurities and then is sent to a semi-finished product storage tank.
Preferably, the method further comprises the following steps:
(1) when the raw oil is a semi-finished product, firstly closing a stop valve on a liquid phase outlet pipeline of the gas-liquid separation zone, feeding the filtered and impurity-removed semi-finished product into a top separation zone from a feeding inlet, and then feeding the semi-finished product to the bottom of an ascending reaction zone through a downcomer;
(2) in the upstream reaction zone, the semi-finished product completes the pre-hydrogenation reaction under the conditions of the existence of a catalyst, the temperature of 200-500 ℃, the pressure of 3.0-25.0 MPa and the volume ratio of hydrogen to oil of 50-2000 to generate an ebullated bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon, and the ebullated bed product flows downwards to a gas-liquid separation zone through a collecting pipe;
(3) the gas-liquid separation is not carried out in the gas-liquid separation zone, and the product of the fluidized bed directly flows downwards to the top of the descending reaction zone through the communicating pipe;
(4) in the downstream reaction zone, the fluidized bed product from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) in the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) in the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
The invention has the beneficial effects that: the hydrogenation device and the hydrogenation method solve the problem that a fixed bed catalyst bed layer is easy to coke and block in the process of processing the raw materials with high impurities and high metal content; the problem that the catalyst is easy to be pulverized to cause the inactivation of the fixed bed catalyst in the process of processing the high-oxygen-content raw material is solved; solves the problem that the conventional fluidized bed or suspended bed can not completely hydrodeoxygenate and remove impurities from the raw materials; solves the problem of large investment of the combination of the conventional boiling bed or the suspension bed and the fixed bed.
Drawings
FIG. 1 is a schematic diagram of the structure of a combined reactor according to the first and third embodiments of the present invention.
FIG. 2 is a schematic diagram of the structure of a combined reactor according to the second and fourth embodiments of the present invention.
FIG. 3 is a schematic structural diagram of a hydrogenation apparatus according to an embodiment of the present invention.
FIG. 4 is a schematic structural diagram of a hydrogenation unit according to the second embodiment of the present invention.
FIG. 5 is a schematic structural diagram of a hydrogenation unit according to the third embodiment of the present invention.
FIG. 6 is a schematic structural diagram of a hydrogenation unit according to the fourth embodiment of the present invention.
The reference signs are: the combined reactor 1, a reactor shell 10, a main feed inlet 101, a main product outlet 102, a raw oil conveying pipeline 103, a pressure reducing valve 104, a semi-finished product conveying pipeline 105, a tail oil conveying pipeline 106, a stop valve 107, a top isolation area 11, a gas-liquid separation area 12, a liquid phase collector 121, a liquid phase outlet 122, an ascending reaction area 13, a boiling bed catalyst bed layer 131, an ascending distribution disc 132, a first hydrogen supplement inlet 133, a descending reaction area 14, a semi-finished product inlet 140, a fixed bed catalyst bed layer 141, a descending distribution disc 142, a second hydrogen supplement inlet 143, an upper sealing disc 151, an interception grid 152, a lower sealing disc 153, a middle sealing disc 154, a descending pipe 16, a communicating pipe 17, a collecting pipe 18, a heavy oil rectifying tower 2, a cold high-pressure separator 3 and a product rectifying tower 4.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying fig. 1-6, which are not intended to limit the present invention.
The conventional boiling point of the present invention refers to the vapor-liquid equilibrium temperature of a substance at one atmosphere pressure.
The conventional gaseous hydrocarbon in the present invention refers to hydrocarbon which is gaseous under conventional conditions, and includes methane, ethane, propane and butane.
The conventional liquid hydrocarbon refers to hydrocarbon which is liquid under the conventional conditions, and comprises pentane and hydrocarbon with higher boiling point.
The specific gravity of the present invention refers to the ratio of the density of a liquid at ordinary pressure and 15.6 ℃ to the density of a liquid at ordinary pressure and 15.6 ℃ unless otherwise specified.
The bio-light oil of the present invention refers to hydrocarbons having a conventional boiling point of less than 180 ℃.
The biodiesel of the invention refers to hydrocarbons with a conventional boiling point of 180-370 ℃.
The impurity component in the present invention refers to a converted matter of a non-hydrocarbon component in a raw material such as water, ammonia, hydrogen sulfide and the like.
The compositions or concentrations or amounts or yields of the components described herein are weight basis values unless otherwise specified.
The term "fluidized bed hydrogenation" as used herein refers to a reaction process of hydrogen consumption of the feedstock oil in the presence of hydrogen and a catalyst at a suitable temperature, wherein the minimum reaction depth has a minimum industrial significance: i.e., the downflow reaction zone (fixed bed hydrogenation section), will generally complete the hydrocracking reaction of the macromolecular hydrocarbons, and will generally complete the deoxygenation reaction of the majority of the oxygenates.
The term fixed bed hydrogenation refers to a reaction process of hydrogen consumption of the hot oil gas and the semi-finished product in the presence of hydrogen and a suitable catalyst, and the lowest reaction depth has the minimum industrial significance: namely qualified biodiesel is produced, and the process generally completes the saturation of all unsaturated bonds in the long-chain structure of the raw material oil; generally, the process will remove all of the oxygen, sulfur and nitrogen from the feed oil.
The ebullated bed catalyst bed of the present invention may also be substituted for one or more of a fixed bed catalyst bed, a suspended bed catalyst bed, an in-line batch displacement bed catalyst bed and a moving bed catalyst bed in combination, and any obvious alternative without departing from the inventive concept is within the scope of the present invention.
Example one
Referring to fig. 1 and 3, a hydrogenation apparatus with coupled ebullated bed and fixed bed comprises a heavy oil rectifying tower 2, a cold high-pressure separator 3, a product rectifying tower 4 and at least one combined reactor 1;
the combined reactor 1 comprises a reactor shell 10, a main feed inlet 101 is arranged at the top of the reactor shell 10, a main product outlet 102 is arranged at the bottom of the reactor shell 10, a top isolation region 11, a gas-liquid separation region 12, an uplink reaction region 13 and a downlink reaction region 14 are sequentially arranged in the reactor shell 10 from top to bottom, an upper sealing disc 151 is arranged between the top isolation region 11 and the gas-liquid separation region 12, an interception grating 152 is arranged between the gas-liquid separation region 12 and the uplink reaction region 13, a lower sealing disc 153 is arranged between the uplink reaction region 13 and the downlink reaction region 14, at least one fluidized bed catalyst bed layer 131 is arranged in the uplink reaction region 13, at least one fixed bed catalyst bed layer 141 is arranged in the downlink reaction region 14, a liquid phase collector 121 is arranged in the gas-liquid separation region 12, a liquid phase outlet 122 communicated with the liquid phase collector 121 is arranged on the outer side wall of the reactor shell 10, a descending pipe 16 is arranged between the top isolation region 11 and the bottom of the uplink reaction region 13, and a communicating pipe 17 is arranged between the gas-liquid phase 12 and the top of the downlink reaction region 14; the outer side wall of the reactor shell 10 corresponding to the position of the ascending reaction zone 13 is provided with at least one first hydrogen supplement inlet 133, and the outer side wall of the reactor shell 10 corresponding to the position of the descending reaction zone 14 is provided with a semi-finished product inlet 140 and at least one second hydrogen supplement inlet 143;
the main feed inlet 101 is connected with a raw oil conveying pipeline 103, the liquid phase outlet 122 is connected with the heavy oil rectifying tower 2, a pressure reducing valve 104 is arranged between the liquid phase outlet 122 and the heavy oil rectifying tower 2, the two liquid phase outlets 122 of the heavy oil rectifying tower 2 are respectively connected with a semi-finished product conveying pipeline 105 and a tail oil conveying pipeline 106, the semi-finished product conveying pipeline 105 is connected with a semi-finished product inlet 140, and the middle part of the tail oil conveying pipeline 106 is connected with the raw oil conveying pipeline 103;
the main product outlet 102 is connected with the inlet of the cold high-pressure separator 3, the liquid phase outlet 122 of the cold high-pressure separator 3 is connected with the inlet of the product rectifying tower 2, and the gas phase outlet of the cold high-pressure separator 3 is respectively connected with the first hydrogen supplement inlet 133, the second hydrogen supplement inlet 143 and the raw oil conveying pipeline 103.
An ascending distribution plate 132 is arranged below each ascending catalyst bed layer 131; a descending distribution plate 142 is arranged above each descending catalyst bed layer 141. The function of the upper distribution plate 132 is: the medium flowing upwards is uniformly distributed on the flow section in the reactor and is uniformly distributed at the bottom of the boiling bed catalyst bed layer 131; the function of the downstream distribution plate 142 is: the downwardly flowing medium is distributed uniformly over the flow cross-section in the reactor, at the top of the fixed bed catalyst bed 141.
The hydrogenation device continuously processes inferior raw materials:
inferior raw oil enters the top of the reactor from the self-feeding inlet 101, is sent to the bottom of the ascending reaction zone 13 (the fluidized bed hydrogenation part) through the downcomer 16, then flows upwards, passes through the fluidized bed catalyst bed 131 to complete pre-hydrogenation, reaches the gas-liquid separation zone 12, completes gas-liquid separation in the gas-liquid separation zone 12, discharges a liquid phase from the liquid phase outlet 122, is sent to the heavy oil separation part after being depressurized through the depressurization valve, is separated into a semi-finished product, tail oil and gas in the heavy oil separation part, mostly returns to the inlet of the ascending reaction zone 13 (the fluidized bed hydrogenation part), discharges a small amount of tail oil, and sends the semi-finished product to the top of the descending reaction zone 14 (the fixed bed hydrogenation part);
the gas phase flows downwards to the top of a descending reaction zone 14 (fixed bed hydrogenation part) through a communicating pipe 17, is mixed with a semi-finished product and then continuously downwards passes through a fixed bed catalyst bed layer 141, flows out through a main product outlet 102, is cooled and then is sent to a cold high-pressure separation part to be separated into three phases of gas, oil and water, most of the gas phase returns to an ascending reaction zone 13 (boiling bed hydrogenation part) and the descending reaction zone 14 (fixed bed hydrogenation part), a small amount of the gas phase is added as a cold hydrogen self-filling hydrogen port, a water phase is discharged to a sewage treatment part, an oil phase is sent to a product separation part, and light bio-oil, biodiesel and non-condensable gas are separated in the product separation part.
A hydrogenation method of a hydrogenation device with coupled ebullated bed and fixed bed comprises the following steps:
(1) Raw oil enters a top isolation region 11 from a main feeding inlet 101 and is sent to the bottom of an upper reaction region 13 (a fluidized bed hydrogenation part) through a downcomer 16;
(2) In the upstream reaction zone 13 (fluidized bed hydrogenation part), the raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the hydrogen/oil volume ratio is 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon; the operating conditions of the hydrogenation part of the boiling bed are preferably as follows: the temperature is 320-450 ℃, the pressure is 8.0-20.0 MPa, and the volume ratio of hydrogen to raw oil is 300-1200;
(3) In the gas-liquid separation zone 12, the boiling bed product is separated into hot oil gas and heavy oil, the hot oil gas is sent to the top of the descending reaction zone 14 (fixed bed hydrogenation part) through a communicating pipe 17, and the heavy oil is sent to the heavy oil separation part after being depressurized through a depressurization valve;
(4) In the heavy oil separation part, the heavy oil is rectified to separate a semi-finished product, tail oil, non-condensable gas and water; at least one part of the semi-finished products are sent to a descending reaction zone 14 (boiling bed hydrogenation part), at least one part of tail oil is returned to an ascending reaction zone 13 (fixed bed hydrogenation part) through a main feeding inlet 101, and the rest part is discharged;
the heavy oil separation section is a step of separating a semi-finished product, tail oil, and noncondensable gas from the liquid phase from the gas-liquid separation zone 12. The liquid phase from the gas-liquid separation zone 12 is firstly reduced in pressure, usually to 0.5-4.0 MPa, to form a gas-liquid mixed phase material flow, then the separation is completed through the processes of separation and/or fractionation, at least a part of tail oil is returned to the fluidized bed hydrogenation part, and at least a part of semi-finished products are sent to the fixed bed hydrogenation part.
(5) In the downstream reaction zone 14 (fixed bed hydrogenation part), the hot oil gas from the gas-liquid separation zone 12 and the semi-finished product from the heavy oil separation part complete hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated; the operating conditions of the fixed bed hydrogenation section are preferably as follows: the temperature is 260-380 ℃, the pressure is 5.0-15.0 MPa, and the space velocity of the hydrogenation catalyst is 0.1-1.0 hr -1 And the volume ratio of hydrogen to raw oil is 500-2000.
(6) In the cold high-pressure separation part, the product of the fixed bed hydrogenation reaction is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least a part of the cold high-molecular gas is returned to the ascending reaction zone 13 (boiling bed hydrogenation part) and the descending reaction zone 14 (fixed bed hydrogenation part) to form circulating hydrogen;
in the cold high-pressure separation section, washing water is generally injected into the reaction product before the fixed-bed hydrogenation reaction product enters the cold high-pressure separator 3. The fixed bed hydrogenation reaction product is usually cooled to below 200 ℃ and then mixed with washing water to form a fixed bed hydrogenation reaction product after water injection. The cold high-pressure separation part comprises the steps of cooling and separating the fixed bed hydrogenation reaction products after water injection. Here, the fixed bed hydrogenation reaction product after water injection is usually cooled to 30 to 70 ℃, and in the cooling process, the fixed bed hydrogenation reaction product after water injection is separated in the cold high-pressure separator 3 into: the high-temperature-resistant oil-gas separator comprises a cold high-temperature-resistant gas mainly composed of hydrogen, a cold high-temperature-resistant oil liquid mainly composed of conventional gas hydrocarbon, conventional liquid hydrocarbon and dissolved hydrogen and a cold high-temperature-resistant water liquid mainly composed of water and dissolved with hydrogen sulfide and ammonia.
As before, at least a portion (usually 80-100%) of the cold high partial gas is returned to the ebullated-bed hydrogenation reaction section and the fixed-bed hydrogenation reaction section to form recycle hydrogen to provide the necessary amount and concentration of hydrogen for the reaction section.
(7) In the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
Example two
Referring to fig. 2 and 4, the present embodiment is different from the first embodiment in that: a top isolation area 11, an uplink reaction area 13, a gas-liquid separation area 12 and a downlink reaction area 14 are sequentially arranged in the reactor shell 10 from top to bottom, an upper sealing disc 151 is arranged between the top isolation area 11 and the uplink reaction area 13, a middle sealing disc 154 is arranged between the uplink reaction area 13 and the gas-liquid separation area 12, a lower sealing disc 153 is arranged between the gas-liquid separation area 12 and the downlink reaction area 14, and a collecting pipe 18 is arranged between the top of the uplink reaction area 13 and the top of the gas-liquid separation area 12.
In the step (2), the boiling bed product flows downwards to the gas-liquid separation zone 12 through the collecting pipe 18.
EXAMPLE III
Referring to fig. 1 and 5, the present embodiment is different from the first embodiment in that: the hydrogenation device cancels the heavy oil rectifying tower 2, the inlet of the cold high-pressure separator 3 is respectively connected with the liquid phase outlet 122 and the main product outlet 102, and a cut-off valve 107 is arranged between the inlet of the cold high-pressure separator 3 and the liquid phase outlet 122.
The hydrogenation device can process the inferior raw material and the semi-finished product respectively by stages, and the processed raw material is switched between the inferior raw material and the semi-finished product by stages.
And (3) processing inferior raw materials: the inferior raw oil enters the top of the reactor from the main feed inlet 101, is sent to the bottom of the ascending reaction zone 13 (the hydrogenation part of the fluidized bed) through the downcomer 16, then flows upwards, passes through the catalyst bed 131 of the fluidized bed to complete pre-hydrogenation, reaches the gas-liquid separation zone 12, completes gas-liquid separation in the gas-liquid separation zone 12, discharges a liquid phase from the liquid phase outlet 122, joins with the material of the main product outlet 102, the gas phase flows downwards to the top of the descending reaction zone 14 (the hydrogenation part of the fixed bed) through the communicating pipe 17, then continuously passes downwards through the catalyst bed 141 of the fixed bed, flows out through the main product outlet 102, joins with the liquid phase from the gas-liquid separation zone 12, is sent to the cold high-pressure separation part after cooling, is separated into three phases of gas, oil and water, most of the gas phase returns to the ascending reaction zone 13 (the hydrogenation part of the fluidized bed) and the descending reaction zone 14 (the hydrogenation part of the fixed bed), a small amount of cold hydrogen is added as a self-hydrogen-filling gas port, discharges the water phase to the sewage treatment part, the oil phase is sent to the product separation part, obtains a semi-finished product after the non-condensable gas is removed from the product separation part, and is sent to the semi-finished product storage tank after filtering and impurity removal.
And (3) processing a semi-finished product: the method comprises the steps of firstly closing a cut-off valve 107 on a liquid phase outlet 122 pipeline of a gas-liquid separation zone 12, enabling a filtered and impurity-removed semi-finished product to enter the top of a reactor through an automatic feeding inlet 101, then sending the semi-finished product to the bottom of an upstream reaction zone 13 (a hydrogenation part of a boiling bed) through a downcomer 16, then enabling the semi-finished product to flow upwards, enabling the semi-finished product to pass through a catalyst bed layer 131 of the boiling bed to complete pre-hydrogenation until the semi-finished product reaches the gas-liquid separation zone 12, enabling all gas phases and liquid phases to flow downwards to the top of a downstream reaction zone 14 (a hydrogenation part of a fixed bed) through a communicating pipe 17 without gas-liquid separation, then enabling all gas phases and liquid phases to continue to flow downwards through a catalyst bed layer 141 of the fixed bed to achieve final hydrogenation of the semi-finished product, enabling the semi-finished product to flow out through a main product outlet 102, cooling and sending the cooled semi-finished product to a cold high-pressure separation part for separation into three phases of gas, enabling most of the gas phases of gas to return to an upstream reaction zone 13 (a hydrogenation part of the boiling bed) and a downstream reaction zone 14 (a fixed bed hydrogenation part), enabling a small amount of cold hydrogen to be added as a self-hydrogen self-charging hydrogen gas phase to be discharged into a sewage treatment part, and enabling an oil phase to be sent to a product separation part, and separated into a product separation part, and light oil, and non-diesel oil and non-condensable gas.
A hydrogenation method of a hydrogenation device with coupled ebullated bed and fixed bed comprises the following steps:
(1) When the raw oil is poor-quality raw oil, the poor-quality raw oil enters the top isolation region 11 from the main feeding inlet 101 and is then conveyed to the bottom of the upper reaction region 13 through the downcomer 16;
(2) In the upward reaction zone 13, the poor-quality raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the volume ratio of hydrogen to oil is 50-2000;
(3) In the gas-liquid separation zone 12, the boiling bed product is separated into hot oil gas and heavy oil, and the hot oil gas is sent to the top of the descending reaction zone 14 through a communicating pipe 17;
(4) In the downstream reaction zone 14, the hot oil gas from the gas-liquid separation zone 12 completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and generates a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon;
(5) In the cold high-pressure separation section, the fixed bed hydrogenation reaction product and the heavy oil from the gas-liquid separation zone 12 are cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least a part of the cold high-molecular gas returns to the ascending reaction zone 13 and the descending reaction zone 14 to form circulating hydrogen;
(6) In the product separation part, the cold high-oil separation liquid is subjected to a rectification process to remove non-condensable gas to obtain a semi-finished product, and the semi-finished product is filtered to remove impurities and then is sent to a semi-finished product storage tank.
Also comprises the following steps:
(1) when the raw oil is a semi-finished product, firstly closing a stop valve 107 on a liquid phase outlet 122 pipeline of the gas-liquid separation zone 12, enabling the filtered and impurity-removed semi-finished product to enter a top isolation zone 11 from a main feeding inlet 101, and then sending the semi-finished product to the bottom of an upper reaction zone 13 through a downcomer 16;
(2) in the ascending reaction zone 13, the semi-finished product completes the pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the volume ratio of hydrogen to oil is 50-2000;
(3) the gas-liquid separation is not carried out in the gas-liquid separation zone 12, and the boiling bed product directly flows downwards to the top of the descending reaction zone 14 through the communicating pipe 17;
(4) in the downstream reaction zone 14, the ebullated bed product from the gas-liquid separation zone 12 completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and generates a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon;
(5) in the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least a part of the cold high-pressure gas returns to the ascending reaction zone 13 and the descending reaction zone 14 to form circulating hydrogen;
(6) in the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
Example four
Referring to fig. 2 and 6, the present embodiment is different from the third embodiment in that: a top isolation area 11, an uplink reaction area 13, a gas-liquid separation area 12 and a downlink reaction area 14 are sequentially arranged in the reactor shell 10 from top to bottom, an upper sealing disc 151 is arranged between the top isolation area 11 and the uplink reaction area 13, a middle sealing disc 154 is arranged between the uplink reaction area 13 and the gas-liquid separation area 12, a lower sealing disc 153 is arranged between the gas-liquid separation area 12 and the downlink reaction area 14, and a collecting pipe 18 is arranged between the top of the uplink reaction area 13 and the top of the gas-liquid separation area 12.
In the step (2), the boiling bed product flows downwards to the gas-liquid separation zone 12 through the collecting pipe 18.
The above-described embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A hydrogenation device with coupled ebullated bed and fixed bed is characterized in that: comprises a heavy oil rectifying tower, a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, a gas-liquid separation region, an uplink reaction region and a downlink reaction region are sequentially arranged in the reactor shell from top to bottom, an upper closed disc is arranged between the top isolation region and the gas-liquid separation region, an interception grid is arranged between the gas-liquid separation region and the uplink reaction region, a lower closed disc is arranged between the uplink reaction region and the downlink reaction region, at least one fluidized bed catalyst bed layer is arranged in the uplink reaction region, at least one fixed bed catalyst bed layer is arranged in the downlink reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the uplink reaction region, and a communicating pipe is arranged between the top of the gas-liquid separation region and the top of the downlink reaction region; the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with a semi-finished product inlet and at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the liquid phase outlet is connected with a heavy oil rectifying tower, a pressure reducing valve is arranged between the liquid phase outlet and the heavy oil rectifying tower, two liquid phase outlets of the heavy oil rectifying tower are respectively connected with a semi-finished product conveying pipeline and a tail oil conveying pipeline, the semi-finished product conveying pipeline is connected with the semi-finished product inlet, and the middle part of the tail oil conveying pipeline is connected with the raw oil conveying pipeline;
the main product outlet is connected with the inlet of the cold high-pressure separator, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplement inlet, the second hydrogen supplement inlet and the raw oil conveying pipeline.
2. The hydrogenation method of an ebullated bed and fixed bed coupled hydrogenation unit of claim 1, wherein: the method comprises the following steps:
(1) Raw oil enters a top isolation region from a main feeding inlet and is then conveyed to the bottom of an upper reaction region through a downcomer;
(2) In the upstream reaction zone, raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the hydrogen/oil volume ratio is 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe, and the heavy oil is depressurized by a depressurization valve and then conveyed to a heavy oil separation part;
(4) In the heavy oil separation part, the heavy oil is rectified to separate a semi-finished product, tail oil, non-condensable gas and water; at least one part of semi-finished products are sent to a descending reaction zone, at least one part of tail oil returns to an ascending reaction zone through a main feeding inlet, and the rest part of tail oil is discharged outside;
(5) In the downstream reaction zone, hot oil gas from the gas-liquid separation zone and a semi-finished product from the heavy oil separation part complete hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(6) In the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of normal gas hydrocarbon, impurity components and normal liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(7) In the product separation part, the cold high-fraction oil liquid is subjected to a rectification process to separate gas, a biological light oil product and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are sent out as products.
3. A hydrogenation device with coupled ebullated bed and fixed bed is characterized in that: comprises a heavy oil rectifying tower, a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, an ascending reaction region, a gas-liquid separation region and a descending reaction region are sequentially arranged in the reactor shell from top to bottom, an upper sealing disc is arranged between the top isolation region and the ascending reaction region, a middle sealing disc is arranged between the ascending reaction region and the gas-liquid separation region, a lower sealing disc is arranged between the gas-liquid separation region and the descending reaction region, at least one fluidized bed catalyst bed layer is arranged in the ascending reaction region, at least one fixed bed catalyst bed layer is arranged in the descending reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the ascending reaction region, a communicating pipe is arranged between the top of the gas-liquid separation region and the top of the gas-liquid separation region; the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with a semi-finished product inlet and at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the liquid phase outlet is connected with a heavy oil rectifying tower, a pressure reducing valve is arranged between the liquid phase outlet and the heavy oil rectifying tower, two liquid phase outlets of the heavy oil rectifying tower are respectively connected with a semi-finished product conveying pipeline and a tail oil conveying pipeline, the semi-finished product conveying pipeline is connected with the semi-finished product inlet, and the middle part of the tail oil conveying pipeline is connected with the raw oil conveying pipeline;
the main product outlet is connected with the inlet of the cold high-pressure separator, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplement inlet, the second hydrogen supplement inlet and the raw oil conveying pipeline.
4. The hydrogenation process of claim 3, wherein the hydrogenation process comprises the steps of: the method comprises the following steps:
(1) Raw oil enters a top isolation region from a main feeding inlet and is then conveyed to the bottom of an upper reaction region through a downcomer;
(2) In the upstream reaction zone, raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the hydrogen/oil volume ratio is 50-2000, so as to generate an ebullated bed product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon, and the ebullated bed product flows downwards to a gas-liquid separation zone through a collecting pipe;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe, and the heavy oil is depressurized by a depressurization valve and then conveyed to a heavy oil separation part;
(4) In the heavy oil separation part, the heavy oil is rectified to separate a semi-finished product, tail oil, non-condensable gas and water; at least one part of the semi-finished products are sent to the descending reaction zone, at least one part of the tail oil returns to the ascending reaction zone through the main feeding inlet, and the rest part is discharged outside;
(5) In the downstream reaction zone, hot oil gas from the gas-liquid separation zone and a semi-finished product from the heavy oil separation part complete hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(6) In the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of normal gas hydrocarbon, impurity components and normal liquid hydrocarbon; at least a part of cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(7) In the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
5. A hydrogenation device with coupled ebullated bed and fixed bed is characterized in that: comprises a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, a gas-liquid separation region, an uplink reaction region and a downlink reaction region are sequentially arranged in the reactor shell from top to bottom, an upper closed disc is arranged between the top isolation region and the gas-liquid separation region, an interception grid is arranged between the gas-liquid separation region and the uplink reaction region, a lower closed disc is arranged between the uplink reaction region and the downlink reaction region, at least one fluidized bed catalyst bed layer is arranged in the uplink reaction region, at least one fixed bed catalyst bed layer is arranged in the downlink reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the uplink reaction region, and a communicating pipe is arranged between the top of the gas-liquid separation region and the top of the downlink reaction region; the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the inlet of the cold high-pressure separator is respectively connected with the liquid phase outlet and the main product outlet, a stop valve is arranged between the inlet of the cold high-pressure separator and the liquid phase outlet, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is respectively connected with the first hydrogen supplementing inlet, the second hydrogen supplementing inlet and the raw oil conveying pipeline.
6. The hydrogenation method of an ebullated bed and fixed bed coupled hydrogenation unit of claim 5, wherein: the method comprises the following steps:
(1) When the raw oil is inferior raw oil, the inferior raw oil enters the top isolation region from the main feeding inlet and is then conveyed to the bottom of the upward reaction region through the downcomer;
(2) In the upstream reaction zone, the inferior raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions of a temperature of 200-500 ℃, a pressure of 3.0-25.0 MPa and a hydrogen/oil volume ratio of 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gaseous hydrocarbon and conventional liquid hydrocarbon;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, and the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe;
(4) In the downstream reaction zone, the hot oil gas from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) In the cold high-pressure separation part, the hydrogenation reaction product of the fixed bed and heavy oil from a gas-liquid separation zone are cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) In the product separation part, the cold high-oil separation liquid is subjected to a rectification process to remove non-condensable gas to obtain a semi-finished product, and the semi-finished product is filtered to remove impurities and then is sent to a semi-finished product storage tank.
7. The hydrogenation process of claim 6, wherein the hydrogenation process comprises the steps of: also comprises the following steps:
(1) when the raw oil is a semi-finished product, firstly closing a stop valve on a liquid phase outlet pipeline of the gas-liquid separation zone, enabling the filtered and impurity-removed semi-finished product to enter a top separation zone from a feeding inlet, and then conveying the semi-finished product to the bottom of an upper reaction zone through a downcomer;
(2) in the upstream reaction zone, the semi-finished product completes the pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the volume ratio of hydrogen to oil is 50-2000, so as to generate a fluidized bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon;
(3) gas-liquid separation is not carried out in the gas-liquid separation zone, and the product of the fluidized bed directly flows downwards to the top of the descending reaction zone through the communicating pipe;
(4) in the downstream reaction zone, the fluidized bed product from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) in the cold high-pressure separation part, the product of the fixed bed hydrogenation reaction is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) in the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
8. A hydrogenation device with coupled ebullated bed and fixed bed is characterized in that: comprises a cold high-pressure separator, a product rectifying tower and at least one combined reactor;
the combined reactor comprises a reactor shell, wherein the top of the reactor shell is provided with a main feeding inlet, the bottom of the reactor shell is provided with a main product outlet, a top isolation region, an uplink reaction region, a gas-liquid separation region and a downlink reaction region are sequentially arranged in the reactor shell from top to bottom, an upper sealing disc is arranged between the top isolation region and the uplink reaction region, a middle sealing disc is arranged between the uplink reaction region and the gas-liquid separation region, a lower sealing disc is arranged between the gas-liquid separation region and the downlink reaction region, at least one fluidized bed catalyst bed layer is arranged in the uplink reaction region, at least one fixed bed catalyst bed layer is arranged in the downlink reaction region, a liquid phase collector is arranged in the gas-liquid separation region, the outer side wall of the reactor shell is provided with a liquid phase outlet communicated with the liquid phase collector, a descending pipe is arranged between the top isolation region and the bottom of the uplink reaction region, a communicating pipe is arranged between the gas-liquid separation region and the top of the downlink reaction region, and a collecting pipe is arranged between the top of the gas-liquid separation region and the top of the gas-liquid separation region;
the outer side wall of the reactor shell is provided with at least one first hydrogen supplement inlet corresponding to the position of the ascending reaction zone, and the outer side wall of the reactor shell is provided with at least one second hydrogen supplement inlet corresponding to the position of the descending reaction zone;
the main feeding inlet is connected with a raw oil conveying pipeline, the inlet of the cold high-pressure separator is connected with the liquid phase outlet and the main product outlet respectively, a stop valve is arranged between the inlet of the cold high-pressure separator and the liquid phase outlet, the liquid phase outlet of the cold high-pressure separator is connected with the inlet of the product rectifying tower, and the gas phase outlet of the cold high-pressure separator is connected with the first hydrogen supplementing inlet, the second hydrogen supplementing inlet and the raw oil conveying pipeline respectively.
9. The hydrogenation process of claim 8 in an ebullated-bed and fixed-bed coupled hydrogenation unit, wherein: the method comprises the following steps:
(1) When the raw oil is inferior raw oil, the inferior raw oil enters the top isolation region from the main feeding inlet and is then conveyed to the bottom of the upward reaction region through the downcomer;
(2) In the upstream reaction zone, the poor-quality raw oil is subjected to a pre-hydrogenation reaction in the presence of a catalyst under the conditions that the temperature is 200-500 ℃, the pressure is 3.0-25.0 MPa and the hydrogen/oil volume ratio is 50-2000, so as to generate an ebullated bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon, and the ebullated bed product flows downwards to a gas-liquid separation zone through a collecting pipe;
(3) In the gas-liquid separation zone, the boiling bed product is separated into hot oil gas and heavy oil, and the hot oil gas is conveyed to the top of the descending reaction zone through a communicating pipe;
(4) In the downstream reaction zone, the hot oil gas from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) In the cold high-pressure separation part, the fixed bed hydrogenation reaction product and the heavy oil from the gas-liquid separation zone are cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) In the product separation part, the cold high-oil separation liquid is subjected to a rectification process to remove non-condensable gas to obtain a semi-finished product, and the semi-finished product is filtered to remove impurities and then is sent to a semi-finished product storage tank.
10. The hydrogenation process of claim 9 in an ebullated bed and fixed bed coupled hydrogenation unit, wherein: also comprises the following steps:
(1) when the raw oil is a semi-finished product, firstly closing a stop valve on a liquid phase outlet pipeline of the gas-liquid separation zone, enabling the filtered and impurity-removed semi-finished product to enter a top separation zone from a feeding inlet, and then conveying the semi-finished product to the bottom of an upper reaction zone through a downcomer;
(2) in the upstream reaction zone, the semi-finished product completes the pre-hydrogenation reaction under the conditions of the existence of a catalyst, the temperature of 200-500 ℃, the pressure of 3.0-25.0 MPa and the volume ratio of hydrogen to oil of 50-2000 to generate an ebullated bed product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon, and the ebullated bed product flows downwards to a gas-liquid separation zone through a collecting pipe;
(3) the gas-liquid separation is not carried out in the gas-liquid separation zone, and the product of the fluidized bed directly flows downwards to the top of the descending reaction zone through the communicating pipe;
(4) in the downstream reaction zone, the fluidized bed product from the gas-liquid separation zone completes hydrogenation reaction in the presence of a catalyst under the conditions of temperature of 200-500 ℃, pressure of 3.0-25.0 MPa and hydrogen/oil volume ratio of 50-2000, and a fixed bed hydrogenation reaction product consisting of hydrogen, water, conventional gas hydrocarbon and conventional liquid hydrocarbon is generated;
(5) in the cold high-pressure separation part, the fixed bed hydrogenation reaction product is cooled and separated into: a cold high-molecular gas mainly composed of hydrogen, a cold high-molecular oil liquid mainly composed of conventional gaseous hydrocarbon, impurity components and conventional liquid hydrocarbon; at least part of the cold high-pressure gas returns to the ascending reaction zone and the descending reaction zone to form circulating hydrogen;
(6) in the product separation part, the cold high-oil separation liquid is rectified to separate gas, biological light oil products and biodiesel, the gas is used as fuel gas of a hydrogenation device, and the biological light oil and the biodiesel are delivered as products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190879.1A CN115404100B (en) | 2022-09-28 | 2022-09-28 | Fluidized bed and fixed bed coupled hydrogenation device and hydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190879.1A CN115404100B (en) | 2022-09-28 | 2022-09-28 | Fluidized bed and fixed bed coupled hydrogenation device and hydrogenation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115404100A true CN115404100A (en) | 2022-11-29 |
| CN115404100B CN115404100B (en) | 2023-10-24 |
Family
ID=84167432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211190879.1A Active CN115404100B (en) | 2022-09-28 | 2022-09-28 | Fluidized bed and fixed bed coupled hydrogenation device and hydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115404100B (en) |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344840A (en) * | 1981-02-09 | 1982-08-17 | Hydrocarbon Research, Inc. | Hydrocracking and hydrotreating shale oil in multiple catalytic reactors |
| US5447621A (en) * | 1994-01-27 | 1995-09-05 | The M. W. Kellogg Company | Integrated process for upgrading middle distillate production |
| CN101591563A (en) * | 2009-06-25 | 2009-12-02 | 中国石油化工集团公司 | The combination process of a kind of boiling bed hydrogenation and fixed bed hydrogenation |
| CN102191072A (en) * | 2010-03-18 | 2011-09-21 | Ifp新能源公司 | Coal conversion process and products, comprising two direct ebullated bed liquefaction stages and a fixed bed hydrocracking stage |
| CN102876364A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Hydrotreatment method |
| WO2013126362A2 (en) * | 2012-02-21 | 2013-08-29 | 4CRGroup LLC | Two-zone, close-coupled, heavy oil hydroconversion process utilizing an ebullating bed first zone |
| CN103789020A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrogenation method of coker gasoline |
| FR3004722A1 (en) * | 2013-04-23 | 2014-10-24 | IFP Energies Nouvelles | PROCESS FOR THE CONVERSION OF FUEL BASED RENEWABLE ORIGINAL LOADS COMPRISING A BOILING BED HYDROTREATMENT STEP AND A FIXED BED HYDROISOMERIZATION STEP |
| CN104388117A (en) * | 2014-11-10 | 2015-03-04 | 陕西延长石油（集团）有限责任公司 | Method for producing high-quality fuel oil by heavy oil hydrocracking |
| US20150361357A1 (en) * | 2013-01-30 | 2015-12-17 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
| CN107815329A (en) * | 2016-09-14 | 2018-03-20 | 中国石化工程建设有限公司 | A kind of method of heavy oil combined hydrogenation |
| CN110878221A (en) * | 2019-12-25 | 2020-03-13 | 陕西延长石油（集团）有限责任公司 | Process for producing low-sulfur marine fuel oil by external circulation type fixed wax oil bed hydrotreatment |
| CN110982552A (en) * | 2019-12-06 | 2020-04-10 | 贺兰增 | Hydrogenation reactor, hydrogenation reaction device and catalytic hydrogenation process |
| CN111378490A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Coal tar full-fraction fluidized bed-fixed bed combined treatment process |
| CN112852478A (en) * | 2021-04-13 | 2021-05-28 | 海南贝朗生物科技有限公司 | Slurry bed and fluidized bed coupled upflow reactor, reactor system and catalytic hydrogenation process |
| CN113337310A (en) * | 2021-06-29 | 2021-09-03 | 海南盈科生物科技有限公司 | Method for preparing biodiesel by deep processing of biomass residual oil |
| CN113416578A (en) * | 2021-07-13 | 2021-09-21 | 海南盈科生物科技有限公司 | Refining method of methyl ester residual oil |
| CN113563923A (en) * | 2021-08-19 | 2021-10-29 | 中国石油化工股份有限公司 | Gasoline hydrogenation method and gasoline hydrogenation device |
| CN214937248U (en) * | 2021-04-02 | 2021-11-30 | 福建省格兰尼生物工程股份有限公司 | Gas-liquid counter-flow reactor |
| CN113755210A (en) * | 2021-09-14 | 2021-12-07 | 洛阳瑞华新能源技术发展有限公司 | Heavy oil series hydroconversion method containing stable bed refining section and fluidized bed cracking section |
| CN113801693A (en) * | 2021-10-15 | 2021-12-17 | 海南盈科生物科技有限公司 | Combined hydrogenation method for fatty acid residue oil |
| TW202216970A (en) * | 2020-10-22 | 2022-05-01 | 大陸商中國石油化工科技開發有限公司 | Multi-phase combination reaction system and reaction method |
-
2022
- 2022-09-28 CN CN202211190879.1A patent/CN115404100B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344840A (en) * | 1981-02-09 | 1982-08-17 | Hydrocarbon Research, Inc. | Hydrocracking and hydrotreating shale oil in multiple catalytic reactors |
| US5447621A (en) * | 1994-01-27 | 1995-09-05 | The M. W. Kellogg Company | Integrated process for upgrading middle distillate production |
| CN101591563A (en) * | 2009-06-25 | 2009-12-02 | 中国石油化工集团公司 | The combination process of a kind of boiling bed hydrogenation and fixed bed hydrogenation |
| CN102191072A (en) * | 2010-03-18 | 2011-09-21 | Ifp新能源公司 | Coal conversion process and products, comprising two direct ebullated bed liquefaction stages and a fixed bed hydrocracking stage |
| CN102876364A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Hydrotreatment method |
| WO2013126362A2 (en) * | 2012-02-21 | 2013-08-29 | 4CRGroup LLC | Two-zone, close-coupled, heavy oil hydroconversion process utilizing an ebullating bed first zone |
| CN103789020A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrogenation method of coker gasoline |
| US20150361357A1 (en) * | 2013-01-30 | 2015-12-17 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
| FR3004722A1 (en) * | 2013-04-23 | 2014-10-24 | IFP Energies Nouvelles | PROCESS FOR THE CONVERSION OF FUEL BASED RENEWABLE ORIGINAL LOADS COMPRISING A BOILING BED HYDROTREATMENT STEP AND A FIXED BED HYDROISOMERIZATION STEP |
| CN104388117A (en) * | 2014-11-10 | 2015-03-04 | 陕西延长石油（集团）有限责任公司 | Method for producing high-quality fuel oil by heavy oil hydrocracking |
| CN107815329A (en) * | 2016-09-14 | 2018-03-20 | 中国石化工程建设有限公司 | A kind of method of heavy oil combined hydrogenation |
| CN111378490A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Coal tar full-fraction fluidized bed-fixed bed combined treatment process |
| CN110982552A (en) * | 2019-12-06 | 2020-04-10 | 贺兰增 | Hydrogenation reactor, hydrogenation reaction device and catalytic hydrogenation process |
| CN110878221A (en) * | 2019-12-25 | 2020-03-13 | 陕西延长石油（集团）有限责任公司 | Process for producing low-sulfur marine fuel oil by external circulation type fixed wax oil bed hydrotreatment |
| TW202216970A (en) * | 2020-10-22 | 2022-05-01 | 大陸商中國石油化工科技開發有限公司 | Multi-phase combination reaction system and reaction method |
| CN214937248U (en) * | 2021-04-02 | 2021-11-30 | 福建省格兰尼生物工程股份有限公司 | Gas-liquid counter-flow reactor |
| CN112852478A (en) * | 2021-04-13 | 2021-05-28 | 海南贝朗生物科技有限公司 | Slurry bed and fluidized bed coupled upflow reactor, reactor system and catalytic hydrogenation process |
| CN113337310A (en) * | 2021-06-29 | 2021-09-03 | 海南盈科生物科技有限公司 | Method for preparing biodiesel by deep processing of biomass residual oil |
| CN113416578A (en) * | 2021-07-13 | 2021-09-21 | 海南盈科生物科技有限公司 | Refining method of methyl ester residual oil |
| CN113563923A (en) * | 2021-08-19 | 2021-10-29 | 中国石油化工股份有限公司 | Gasoline hydrogenation method and gasoline hydrogenation device |
| CN113755210A (en) * | 2021-09-14 | 2021-12-07 | 洛阳瑞华新能源技术发展有限公司 | Heavy oil series hydroconversion method containing stable bed refining section and fluidized bed cracking section |
| CN113801693A (en) * | 2021-10-15 | 2021-12-17 | 海南盈科生物科技有限公司 | Combined hydrogenation method for fatty acid residue oil |
Non-Patent Citations (3)
| Title |
|---|
| MENG ZHAOHUI ET AL: ""Experimental Study of Integrated Ebullated-bed and Fixed-bed for Hydrotreating Mid-Low Temperature Coal Tar to Clean Fuel"", 《CHINA PETROLEUM PROCESSING AND PETROCHEMICAL TECHNOLOGY》, vol. 18 * |
| 叶正才: ""固定床加氢反应器内件的结构及应用"", 《化学工程与装备》, no. 07 * |
| 孟兆会等: ""沸腾床与固定床组合工艺加氢处理煤焦油试验研究"", 《煤炭科学技术》, vol. 43 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115404100B (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102191072B (en) | Comprise coal method for transformation and the product of fixed bed hydrogenation cleavage stages and two direct ebullated bed liquefaction stages | |
| CN1876767B (en) | Coal tar hydrocracking method | |
| JP6501898B2 (en) | Diesel fuel and jet fuel production system and method using Fischer-Tropsch synthetic oil | |
| CN113337310B (en) | Method for preparing biodiesel by deep processing of biomass residual oil | |
| CN112048340A (en) | Method for producing second-generation biodiesel and aviation fuel by three-step combined process | |
| CN102786986A (en) | Refining technology of microalgae pyrolysis oil | |
| CN103224835A (en) | Method for extraction of unsaturated fatty acid from oil-containing microalgae and preparation of aviation fuels | |
| CN105567316A (en) | Tinpot heavy oil processing and treating method | |
| CN105524667B (en) | Aviation alternative fuel and preparation method thereof | |
| CN106906001B (en) | Method for co-processing coal with high content of inert components and heavy oil | |
| CN105647581A (en) | Catalytic gasoline hydrogenation method | |
| CN103484159B (en) | Matching technology method for optimizing feeding of coal tar suspended bed hydrocracker | |
| CN101962572A (en) | Coal tar heavy fraction fluidized-bed hydrocracking method and system thereof | |
| CN106635152B (en) | A kind of processing method of full fraction of coal tar oil | |
| CN110028985A (en) | A kind of method that biomass pyrolysis liquid prepares high-quality fuel oil and/or industrial chemicals | |
| CN203559012U (en) | Coal tar treatment system | |
| CN205152158U (en) | Coal tar suspension bed hydrocracking unit | |
| CN105038853A (en) | Method for utilizing FCC slurry and coal to co-refine oil | |
| CN109355100B (en) | Coal tar processing and coal co-refining combined process | |
| CN101892064A (en) | Coal tar separation method | |
| CN115404100B (en) | Fluidized bed and fixed bed coupled hydrogenation device and hydrogenation method | |
| CN102311782B (en) | Method for producing diesel oil by purifying coal tar through hydrogenating | |
| CN102041068B (en) | Hydrofining method of secondarily processed gasoline fractions | |
| CN113801693B (en) | Combined hydrogenation method for fatty acid residue oil | |
| CN113416578B (en) | Refining method of methyl ester residual oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |