CN113234475A - Heavy inferior oil hydro-thermal cracking device and method - Google Patents
Heavy inferior oil hydro-thermal cracking device and method Download PDFInfo
- Publication number
- CN113234475A CN113234475A CN202110630598.2A CN202110630598A CN113234475A CN 113234475 A CN113234475 A CN 113234475A CN 202110630598 A CN202110630598 A CN 202110630598A CN 113234475 A CN113234475 A CN 113234475A
- Authority
- CN
- China
- Prior art keywords
- pressure
- separation
- oil
- unit
- hydro
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 247
- 238000006243 chemical reaction Methods 0.000 claims abstract description 143
- 239000001257 hydrogen Substances 0.000 claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 78
- 239000002904 solvent Substances 0.000 claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 47
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims description 149
- 239000007788 liquid Substances 0.000 claims description 39
- 239000000852 hydrogen donor Substances 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000010724 circulating oil Substances 0.000 claims description 25
- 239000000295 fuel oil Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 20
- 230000006837 decompression Effects 0.000 claims description 19
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 17
- 230000000087 stabilizing effect Effects 0.000 claims description 15
- 239000003849 aromatic solvent Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000003079 shale oil Substances 0.000 claims description 8
- 125000002619 bicyclic group Chemical group 0.000 claims description 7
- 239000011280 coal tar Substances 0.000 claims description 7
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000000571 coke Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000003367 polycyclic group Chemical group 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 81
- 238000004939 coking Methods 0.000 abstract description 14
- 239000007795 chemical reaction product Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000008676 import Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- -1 combinations of Co Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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 provides a heavy inferior oil hydro-thermal cracking device and a method thereof, wherein the device comprises a hydro-thermal cracking reaction unit, a high-low pressure separation unit and a product separation unit which are sequentially connected, the hydro-thermal cracking reaction unit comprises at least one stage of fully-mixed suspended bed reactor, an inlet of the hydro-thermal cracking reaction unit is connected with a hydrogen supply solvent feeding pipeline, and a side draw outlet of the product separation unit is connected with an inlet of the hydro-thermal cracking reaction unit. The device takes the reaction unit and the separation unit as main bodies, adopts the suspension bed reactor to realize hydrogenation lightening of heavy inferior oil, takes the hydrogen supply solvent as an auxiliary raw material, can effectively inhibit coking reaction, fully separates and recycles reaction products through the separation unit, and integrally improves the conversion rate of the heavy inferior oil and the yield of light oil products; the device has the advantages of simple structure, simple process route and low coking tendency, is favorable for long-period stable operation of the device, and improves the production efficiency.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a device and a method for hydro-thermal cracking heavy inferior oil.
Background
The petroleum resource components are complex, so heavy and poor components are inevitably generated in the processing process, and the heavy and poor oil components are complex, so that the contents of carbon residue, metal and asphaltene are high, and the heavy and poor oil contains sulfur, nitrogen and other heteroatom substances, so that the resource value is reduced and the environment is greatly polluted when the heavy and poor oil is directly used as a fuel. The processing technology developed for inferior oil, such as delayed coking, has the problems of high coke yield, low energy utilization rate, coking pollution and the like, so the lightening of heavy inferior oil is one of the important processing routes and is also one of the key research directions of the current petrochemical industry.
The suspension bed hydrogenation and lightening process is an important processing mode of heavy inferior oil, and the suspension bed hydrogenation process enables highly dispersed fine particle catalysts or additives, raw oil and hydrogen to pass through a reactor together, so that the method is an inferior heavy oil deep processing method with low investment and operation cost, and has the characteristics of strong raw material adaptability, simple process, high demetalization rate and the like, but the conventional suspension bed hydrogenation process still has the problems of limited heavy oil conversion rate and high solid content in products.
CN 107177372a discloses a suspension bed hydrogenation method of heavy oil raw material, which comprises the following steps: feeding reaction feed comprising a heavy oil raw material, hydrogen and an adsorbent into a reaction unit to perform a suspension bed hydrogenation reaction to obtain a hydrogenation product; the reaction unit comprises a plurality of suspension bed hydrogenation reactors connected in series; the adsorbent is a porous carbonaceous material; the method mainly discloses a reaction unit for heavy oil hydrogenation, emphasizes the function of an adsorbent, but does not specify the operation unit of the whole system, and does not relate to the type and source of raw materials and the separation of products.
CN 104109558A discloses a two-stage type hydrogenation refining method for inferior oil, which comprises the steps of firstly, carrying out mild hydrocracking reaction on the inferior oil by adopting a first slurry bed reactor, and carrying out gas-liquid separation on a hydrogenation reaction product during the reaction; the separated liquid phase material is mixed with hydrogen and then sent into a second slurry bed reactor for further hydrogenation reaction, the outlet material is subjected to gas-liquid separation again, and the obtained solid heavy residual oil is subjected to reduced pressure distillation; the method adopts a two-stage slurry bed reactor to carry out gas-phase on-line hydrofining on the inferior oil, and the hydrogenation process steps of the method are more complicated and do not involve the use of solvent oil.
In summary, for the light treatment of heavy and poor oil, it is necessary to select a suitable apparatus combination and process method to realize the efficient conversion of heavy and poor oil and realize the long-period stable operation of the apparatus.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a heavy inferior oil hydro-thermal cracking device and a method, wherein the device mainly comprises a reaction unit and a separation unit, a hydrogen supply solvent is used as an auxiliary reaction raw material, a suspension bed reactor is adopted to realize the hydrogenation and lightening of the heavy inferior oil, the coking tendency is low, the heavy oil conversion rate is high, the content of solid unconverted oil is less, and the long-period stable operation of the device is facilitated.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a heavy inferior oil hydrocracker, which comprises a hydrocracker reaction unit, a high-low pressure separation unit and a product separation unit, wherein the hydrocracker reaction unit comprises at least one stage of fully mixed suspended bed reactor, the inlet of the hydrocracker reaction unit is connected with a hydrogen supply solvent feeding pipeline, the outlet at the top of the hydrocracker reaction unit is connected with the inlet of the high-low pressure separation unit, the liquid phase outlet of the high-low pressure separation unit is connected with the inlet of the product separation unit, and the side draw outlet of the product separation unit is connected with the inlet of the hydrocracker reaction unit.
In the invention, for the light treatment of heavy inferior oil, a full-mixed suspension bed reactor is adopted for hydro-thermal cracking reaction, a hydrogen supply solvent is added into reaction raw materials, so that the diffusion of the raw materials such as hydrogen and the like and the hydro-conversion of the heavy inferior oil can be effectively promoted, the occurrence of coking reaction can be effectively inhibited, and reaction products are fully separated and recycled through a high-low pressure separation and product separation unit, so that the conversion rate of the heavy inferior oil and the yield of a light oil product are improved; the device has the advantages of simple structure, simple and convenient operation, high treatment efficiency and wide application prospect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the number of stages of the fully mixed type suspension bed reactor is 1-3 stages, such as 1 stage, 2 stages or 3 stages.
Preferably, the top outlet of the previous stage of fully-mixed suspended bed reactor is connected with the bottom inlet of the next stage of fully-mixed suspended bed reactor.
Preferably, the bottom of each stage of the fully mixed suspension bed reactor is provided with a circulating loop.
Preferably, the circulating loops are provided with circulating pumps.
In the invention, the hydrocracking reaction unit is provided with a multi-stage fully-mixed suspension bed reactor, and reactant hydrogen can be added into each stage of reactor to ensure that the hydrogen is quickly saturated and avoid the easy condensation coking reaction caused by insufficient hydrogen; and the bottom of the suspension bed reactor is subjected to light circulation by adopting a circulating pump, so that the mass transfer and heat transfer in the reactor are enhanced, the temperature distribution is uniform, the coking reaction is inhibited, and the yield of oil products is effectively improved.
As a preferable technical scheme of the invention, the high-low pressure separation unit comprises a hot high-pressure separator, a warm high-pressure separator, a cold high-pressure separator, a hot medium-pressure separator, a warm medium-pressure separator and a cold low-pressure separator, wherein the separators in the high-low pressure separation unit are divided into two branches, an upper outlet of the hot high-pressure separator is sequentially connected with the warm high-pressure separator and the cold high-pressure separator, and a lower outlet of the hot high-pressure separator is sequentially connected with the warm medium-pressure separator, the warm medium-pressure separator and the cold low-pressure separator.
Preferably, the lower outlet of the warm high-pressure separator and the upper outlet of the hot medium-pressure separator are both connected to the inlet of the warm medium-pressure separator, the upper outlet of the cold high-pressure separator is connected to the hydro-thermal cracking reaction unit, the lower outlet of the cold high-pressure separator is connected to the inlet of the cold low-pressure separator, and the lower outlets of the hot medium-pressure separator, the warm medium-pressure separator and the cold low-pressure separator are all connected to the product separation unit.
Preferably, the apparatus further comprises a hydrogen compression unit disposed on the circulation line of the separation gas of the high-and low-pressure separation unit.
In the invention, the high-pressure and low-pressure separation unit comprises a multi-stage separator, wherein the selection of the separator and the arrangement of the connection relation are mainly based on the composition characteristics of reaction products and the technological conditions required by gas-liquid separation, the separation is carried out according to the difference of operation temperature and pressure, the gas-phase components in the reaction products are fully separated, and the circulating hydrogen is returned to be used as the hydrogenation reaction raw material, so that the utilization rate of the hydrogen is improved.
As a preferable technical scheme, the product separation unit comprises a stabilizing tower and a decompression tower which are sequentially connected, wherein a light oil product is extracted from a top outlet of the decompression tower, circulating oil is extracted from a side outlet of the decompression tower, and solid unconverted oil is extracted from a bottom outlet of the decompression tower.
Preferably, the device also comprises a mixed feeding unit, and the outlet of the mixed feeding unit is connected with the inlet of the hydrocracking reaction unit.
Preferably, the hydrogen supply solvent feeding pipeline, the circulating pipeline of the high-low pressure separation unit and the circulating pipeline of the product separation unit are all connected to the mixed feeding unit.
In the invention, the product is fractionated according to the selection of product separation unit equipment and the composition of reaction products, and for the part of non-light oil products, except for bottom fraction with high solid content, the residual cycle oil as hydrogenation product can also be used as hydrogen supply solvent for recycling so as to improve the conversion rate of raw materials.
In another aspect, the present invention provides a method for hydro-thermal cracking heavy inferior oil by using the above apparatus, the method comprising the steps of:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen donor solvent, and then carrying out a hydro-thermal cracking reaction to obtain a hydrogenation product;
(2) and (3) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1) to obtain a light oil product and circulating oil, and returning the circulating oil to the step (1) for reaction again.
As a preferred technical solution of the present invention, the heavy inferior oil in step (1) includes any one or a combination of at least two of vacuum residue, coal tar heavy fraction, shale oil-based heavy oil fraction, solid coke-containing heavy oil fraction, and pulverized coal-blended heavy oil fraction, and the combination is typically but not limited to: the combination of the vacuum residue and the coal tar heavy fraction, the combination of the shale oil-based heavy oil fraction and the heavy oil fraction containing the solid coke breeze, the combination of the vacuum residue, the coal tar heavy fraction and the shale oil-based heavy oil fraction, the combination of the shale oil-based heavy oil fraction, the heavy oil fraction containing the solid coke breeze and the heavy oil fraction mixed with the pulverized coal, and the like.
Wherein the mass fraction of the coal dust in the heavy oil fraction blended with the coal dust is 20-50 wt%, such as 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%.
Preferably, the active component of the catalyst of step (1) comprises any one or a combination of at least two of Fe, Co, Ni or Mo, typical but non-limiting examples of which are: combinations of Fe and Co, combinations of Ni and Mo, combinations of Fe, Co and Ni, combinations of Co, Ni and Mo, and the like.
Preferably, the hydrogen donor solvent in step (1) comprises any one of or a combination of at least two of paraffinic solvent oil, bicyclic aromatic solvent oil or polycyclic aromatic solvent oil, and typical but non-limiting examples of the combination are: a combination of a paraffinic solvent oil and a bicyclic aromatic solvent oil, a combination of a bicyclic aromatic solvent oil and a polycyclic aromatic solvent oil, a combination of a paraffinic solvent oil, a bicyclic aromatic solvent oil, and a polycyclic aromatic solvent oil, and the like.
Preferably, the hydrogen donating solvent of step (1) has a hydrogen donating index of not less than 20, such as 20, 22, 25, 27, 30, 32, 35, or 40, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the weight ratio of the heavy inferior oil, the catalyst and the hydrogen donor solvent in the step (1) is 1:0.01 to 0.05 (0.3 to 1.5), such as 1:0.01:0.3, 1:0.01:0.8, 1:0.01:1.5, 1:0.03:0.4, 1:0.03:1, 1:0.03:1.5, 1:0.05:0.3, 1:0.05:0.6, 1:0.05:1.2 or 1:0.05:1.5, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
As a preferable technical scheme of the invention, the hydrogen donor solvent in the step (1) is prepared by adopting a fixed bed hydrogenation reactor.
Preferably, the hydrogen donor solvent is prepared by shallow hydrogenation of 250-420 ℃ distillate oil of petroleum, coal tar or shale oil, such as 250 ℃, 270 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃ or 420 ℃ and the like.
Preferably, the active component of the catalyst used in the preparation of the hydrogen donating solvent comprises any one of Co, Ni or Mo or a combination of at least two of these, typical but non-limiting examples being: combinations of Co and Ni, combinations of Ni and Mo, combinations of Co, Ni and Mo, and the like.
Preferably, the reaction temperature for the preparation of the hydrogen donor solvent is 220 to 380 ℃, for example 220 ℃, 240 ℃, 270 ℃, 300 ℃, 320 ℃, 350 ℃ or 380 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction pressure for the preparation of the hydrogen donor solvent is 10 to 16MPaG, such as 10MPaG, 11MPaG, 12MPaG, 13MPaG, 14MPaG, 15MPaG or 16MPaG, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the hydrogen donor solvent prepared by the process has high hydrogen donor index PDQI and strong hydrogen donor capacity, and is beneficial to the hydrogenation conversion of heavy oil.
As a preferred embodiment of the present invention, the temperature of the reaction raw materials after mixing in the step (1) is 350 to 420 ℃, for example, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 400 ℃, 410 ℃, or 420 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.
Preferably, the hydrocracked reaction of step (1) is carried out in at least one stage of a fully mixed suspended bed reactor.
Preferably, the hydrogen is introduced into each stage of the fully mixed suspension bed reactor.
Preferably, the temperature of the hydrocracker reaction in step (1) is 420 to 480 ℃, for example 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃ or 480 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the pressure of the hydrocracked reaction in step (1) is 15 to 25MPaG, such as 15MPaG, 16MPaG, 18MPaG, 20MPaG, 22MPaG, 24MPaG or 25MPaG, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the hydrocracked reaction in step (1) has a total hydrogen to oil volume ratio of (500-1500): 1, for example 500:1, 600:1, 800:1, 1000:1, 1200:1, 1400:1 or 1500:1, but not limited to the recited values, and other values not recited in this range are also applicable.
In the invention, the hydrogen-oil volume ratio refers to the volume ratio of the added hydrogen to the raw oil, and the raw oil refers to the mixture of the heavy inferior oil and the hydrogen donor solvent.
As a preferable technical scheme of the invention, the gas-liquid separation in the step (2) adopts a step separation mode, which comprises hot high-pressure separation, warm high-pressure separation, cold high-pressure separation, hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, wherein the product of the hot high-pressure separation is divided into two parts, one part is sequentially subjected to the warm high-pressure separation and the cold high-pressure separation, and the other part is sequentially subjected to the hot medium-pressure separation, the warm medium-pressure separation and the cold low-pressure separation.
Preferably, the operating temperature of the hot high-pressure separation is 350 to 420 ℃, for example 350 ℃, 360 ℃, 380 ℃, 400 ℃ or 420 ℃, the operating temperature of the hot high-pressure separation is 250 to 280 ℃, for example 250 ℃, 260 ℃, 270 ℃ or 280 ℃, and the operating temperature of the cold high-pressure separation is 40 to 50 ℃, for example 40 ℃, 42 ℃, 45 ℃, 48 ℃ or 50 ℃, but not limited to the recited values, and other values not recited within the respective numerical ranges are also applicable.
Preferably, the operating pressure of the hot high-pressure separation, the warm high-pressure separation and the cold high-pressure separation is 16 to 25MPa, such as 16MPa, 17MPa, 18MPa, 20MPa, 21MPa, 22MPa, 24MPa or 25MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the hot medium pressure separation is carried out at an operating temperature of 320 to 410 ℃, for example 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃ or 410 ℃ and at an operating pressure of 3.0 to 6.0MPa, for example 3.0MPa, 4.0MPa, 5.0MPa or 6.0MPa, but not limited to the recited values, and other values not recited within the respective numerical ranges are equally applicable.
Preferably, the warm medium pressure separation is carried out at an operating temperature of 180 to 250 ℃, for example 180 ℃, 200 ℃, 220 ℃, 240 ℃ or 250 ℃ and at an operating pressure of 3.0 to 6.0MPa, for example 3.0MPa, 4.0MPa, 5.0MPa or 6.0MPa, but not limited to the recited values, and other values not recited within the respective numerical ranges are equally applicable.
Preferably, the cold low-pressure separation is carried out at an operating temperature of 40 to 50 ℃, for example 40 ℃, 42 ℃, 45 ℃, 48 ℃ or 50 ℃ and the like, and at an operating pressure of 2.0 to 3.0MPa, for example 2.0MPa, 2.2MPa, 2.5MPa, 2.7MPa or 3.0MPa and the like, but not limited to the recited values, and other values not recited within the respective numerical ranges are also applicable.
Preferably, the gas obtained by gas-liquid separation is compressed and then returned to the step (1) for reuse.
As a preferred embodiment of the present invention, the liquid-liquid separation in step (2) comprises: and (4) separating by adopting a reduced pressure distillation mode.
Preferably, the pressure reduction is carried out in sequence through a stabilizer column having an operating pressure of 0.2 to 0.6MPa, such as 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6MPa, and a vacuum column having an operating pressure of 5 to 25kPa, such as 5kPa, 8kPa, 10kPa, 15kPa, 20kPa or 25kPa, but not limited to the recited values, and other values not recited within the respective ranges of values are also applicable.
In the invention, the stabilizing tower in the product separation unit mainly has the functions of removing dissolved hydrogen, sulfur-containing dry gas and the like in the hydrogenation product and avoiding the influence on the separation components of the vacuum tower.
Preferably, the reduced pressure distillation is carried out mainly in a reduced pressure column, and the operating temperature is 50 to 360 ℃, for example, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ or 360 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the product of the liquid-liquid separation in step (2) further comprises solid-containing unconverted oil.
Preferably, the weight ratio of the recycled oil returned after the liquid-liquid separation in the step (2) to the heavy and low-quality oil in the step (1) is (0.2 to 0.5):1, for example, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1 or 0.5:1, but the present invention is not limited to the recited values, and other values not recited in the above range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) the device of the invention takes the reaction unit and the separation unit as main bodies, adopts the suspension bed reactor to realize hydrogenation lightening of heavy inferior oil, takes a hydrogen supply solvent as an auxiliary reaction raw material, can effectively inhibit coking reaction, and then fully separates and recycles reaction products through the high-low pressure separation and product separation unit, thereby integrally improving the conversion rate of the heavy inferior oil and the yield of the light oil product, wherein the conversion rate of the former reaches more than 95 percent, and the yield of the latter reaches more than 92 percent;
(2) the device provided by the invention has the advantages of simple structure, simple process route and low coking tendency, and is beneficial to realizing long-period stable operation of the device, reducing the production cost and improving the production efficiency.
Drawings
FIG. 1 is a schematic structural diagram of a hydrocracking apparatus for heavy inferior oil provided in example 1 of the present invention;
FIG. 2 is a schematic structural diagram of a high-low pressure separation unit provided in example 1 of the present invention;
the system comprises a 1-mixed feeding unit, a 2-hydrocracked reaction unit, a 3-high-low pressure separation unit, a 31-hot high-pressure separator, a 32-warm high-pressure separator, a 33-cold high-pressure separator, a 34-hot medium-pressure separator, a 35-warm medium-pressure separator, a 36-cold low-pressure separator, a 4-product separation unit and a 5-hydrogen compression unit.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The device comprises a hydro-thermal cracking reaction unit 2, a high-low pressure separation unit 3 and a product separation unit 4, wherein the hydro-thermal cracking reaction unit 2 comprises at least one stage of fully-mixed suspended bed reactor, an inlet of the hydro-thermal cracking reaction unit 2 is connected with a hydrogen supply solvent feeding pipeline, a top outlet of the hydro-thermal cracking reaction unit 2 is connected with an inlet of the high-low pressure separation unit 3, a liquid phase outlet of the high-low pressure separation unit 3 is connected with an inlet of the product separation unit 4, and a side draw outlet of the product separation unit 4 is connected with an inlet of the hydro-thermal cracking reaction unit 2.
The method comprises the following steps:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen donor solvent, and then carrying out a hydro-thermal cracking reaction to obtain a hydrogenation product;
(2) and (3) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1) to obtain a light oil product and circulating oil, and returning the circulating oil to the step (1) for reaction again.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a heavy inferior oil hydrocracker, the structural schematic diagram of the device is shown in fig. 1, and the device comprises a hydrocracker reaction unit 2, a high-low pressure separation unit 3 and a product separation unit 4, the hydrocracker reaction unit 2 comprises a three-stage fully-mixed suspended bed reactor, an inlet of the hydrocracker reaction unit 2 is connected with a hydrogen supply solvent feeding pipeline, a top outlet of the hydrocracker reaction unit 2 is connected with an inlet of the high-low pressure separation unit 3, a liquid phase outlet of the high-low pressure separation unit 3 is connected with an inlet of the product separation unit 4, and a side draw outlet of the product separation unit 4 is connected with an inlet of the hydrocracker reaction unit 2.
The top outlet of the previous stage of fully mixed type suspended bed reactor in the hydrocracking reaction unit 2 is connected with the bottom inlet of the next stage of fully mixed type suspended bed reactor.
And a circulating loop is arranged at the bottom of each stage of the fully mixed type suspended bed reactor, and circulating pumps are arranged on the circulating loops.
The structure schematic diagram of high-low pressure separator unit 3 is as shown in fig. 2, including hot high pressure separator 31, warm high pressure separator 32, cold high pressure separator 33, hot medium pressure separator 34, warm medium pressure separator 35 and cold low pressure separator 36, the separator in high-low pressure separator unit 3 is divided into two, warm high pressure separator 32, cold high pressure separator 33 are connected in proper order to the upper portion export of hot high pressure separator 31, hot medium pressure separator 34, warm medium pressure separator 35 and cold low pressure separator 36 are connected in proper order to the lower part export of hot high pressure separator 31.
The lower outlet of the warm high-pressure separator 32 and the upper outlet 34 of the hot medium-pressure separator are connected to the inlet of the warm medium-pressure separator 35, the upper outlet of the cold high-pressure separator 33 is connected to the hydrocracking reaction unit 2, the lower outlet of the cold high-pressure separator 33 is connected to the inlet of the cold low-pressure separator 36, and the lower outlets of the warm medium-pressure separator 34, the warm medium-pressure separator 35 and the cold low-pressure separator 36 are connected to the product separation unit 4.
The device also comprises a hydrogen compression unit 5, and the hydrogen compression unit 5 is arranged on a circulation pipeline of the separated gas of the high-low pressure separation unit 3.
The product separation unit 4 comprises a stabilizing tower and a decompression tower which are sequentially connected, a light oil product is extracted from an outlet at the top of the decompression tower, circulating oil is extracted from a side outlet of the decompression tower, and solid unconverted oil is extracted from an outlet at the bottom of the decompression tower.
The device also comprises a mixed feeding unit 1, wherein an outlet of the mixed feeding unit 1 is connected with an inlet of the hydrocracking reaction unit 2; and the hydrogen supply solvent feeding pipeline, the circulating pipeline of the high-low pressure separation unit 3 and the circulating pipeline of the product separation unit 4 are connected to the mixed feeding unit 1.
Example 2:
the embodiment provides a heavy inferior oil hydrocracker, the device includes hydrocracker reaction unit 2, high and low pressure separation unit 3 and product separation unit 4, hydrocracker reaction unit 2 includes two-stage complete mixing type suspension bed reactor, hydrocracker reaction unit 2's access connection has the hydrogen supply solvent feed line, hydrocracker reaction unit 2's top export links to each other with high and low pressure separation unit 3's import, high and low pressure separation unit 3's liquid phase outlet links to each other with product separation unit 4's import, product separation unit 4's side draw export links to each other with hydrocracker reaction unit 2's import.
The top outlet of the previous stage of fully mixed type suspended bed reactor in the hydrocracking reaction unit 2 is connected with the bottom inlet of the next stage of fully mixed type suspended bed reactor.
And a circulating loop is arranged at the bottom of each stage of the fully mixed type suspended bed reactor, and circulating pumps are arranged on the circulating loops.
High low pressure separator unit 3 includes hot high pressure separator 31, warm high pressure separator 32, cold high pressure separator 33, hot medium pressure separator 34, warm medium pressure separator 35 and cold low pressure separator 36, the separator in high low pressure separator unit 3 is divided into two, warm high pressure separator 32, cold high pressure separator 33 are connected in proper order to the upper portion export of hot high pressure separator 31, hot medium pressure separator 34, warm medium pressure separator 35 and cold low pressure separator 36 are connected in proper order to the lower part export of hot high pressure separator 31.
The lower outlet of the warm high-pressure separator 32 and the upper outlet 34 of the hot medium-pressure separator are connected to the inlet of the warm medium-pressure separator 35, the upper outlet of the cold high-pressure separator 33 is connected to the hydrocracking reaction unit 2, the lower outlet of the cold high-pressure separator 33 is connected to the inlet of the cold low-pressure separator 36, and the lower outlets of the warm medium-pressure separator 34, the warm medium-pressure separator 35 and the cold low-pressure separator 36 are connected to the product separation unit 4.
The product separation unit 4 comprises a stabilizing tower and a decompression tower which are sequentially connected, a light oil product is extracted from an outlet at the top of the decompression tower, circulating oil is extracted from a side outlet of the decompression tower, and solid unconverted oil is extracted from an outlet at the bottom of the decompression tower.
The device also comprises a mixed feeding unit 1, wherein an outlet of the mixed feeding unit 1 is connected with an inlet of the hydrocracking reaction unit 2; and the hydrogen supply solvent feeding pipeline, the circulating pipeline of the high-low pressure separation unit 3 and the circulating pipeline of the product separation unit 4 are connected to the mixed feeding unit 1.
Example 3:
the embodiment provides a heavy inferior oil hydrocracker, the device is including hydrocracker reaction unit 2, high and low pressure separation unit 3 and product separation unit 4, hydrocracker reaction unit 2 includes level four complete mixing type suspended bed reactor, hydrocracker reaction unit 2's access connection has the hydrogen supply solvent feed line, the top export of hydrocracker reaction unit 2 links to each other with high and low pressure separation unit 3's import, high and low pressure separation unit 3's liquid phase outlet links to each other with product separation unit 4's import, product separation unit 4's side draw export links to each other with hydrocracker reaction unit 2's import.
The top outlet of the previous stage of fully mixed type suspended bed reactor in the hydrocracking reaction unit 2 is connected with the bottom inlet of the next stage of fully mixed type suspended bed reactor.
And a circulating loop is arranged at the bottom of each stage of the fully mixed type suspended bed reactor, and circulating pumps are arranged on the circulating loops.
High low pressure separator unit 3 includes hot high pressure separator 31, warm high pressure separator 32, cold high pressure separator 33, hot medium pressure separator 34, warm medium pressure separator 35 and cold low pressure separator 36, the separator in high low pressure separator unit 3 is divided into two, warm high pressure separator 32, cold high pressure separator 33 are connected in proper order to the upper portion export of hot high pressure separator 31, hot medium pressure separator 34, warm medium pressure separator 35 and cold low pressure separator 36 are connected in proper order to the lower part export of hot high pressure separator 31.
The lower outlet of the warm high-pressure separator 32 and the upper outlet 34 of the hot medium-pressure separator are connected to the inlet of the warm medium-pressure separator 35, the upper outlet of the cold high-pressure separator 33 is connected to the hydrocracking reaction unit 2, the lower outlet of the cold high-pressure separator 33 is connected to the inlet of the cold low-pressure separator 36, and the lower outlets of the warm medium-pressure separator 34, the warm medium-pressure separator 35 and the cold low-pressure separator 36 are connected to the product separation unit 4.
The device also comprises a hydrogen compression unit 5, and the hydrogen compression unit 5 is arranged on a circulation pipeline of the separated gas of the high-low pressure separation unit 3.
The product separation unit 4 comprises a stabilizing tower and a decompression tower which are sequentially connected, a light oil product is extracted from an outlet at the top of the decompression tower, circulating oil is extracted from a side outlet of the decompression tower, and solid unconverted oil is extracted from an outlet at the bottom of the decompression tower.
Example 4:
the embodiment provides a hydro-thermal cracking method for heavy inferior oil, which is carried out by adopting the device in the embodiment 1 and comprises the following steps:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen supply solvent, wherein the heavy inferior oil is vacuum residue oil, the active component of the catalyst is Fe, the hydrogen supply solvent is alkane solvent oil, the hydrogen supply index of the alkane solvent oil is 25, the weight ratio of the heavy inferior oil, the catalyst and the hydrogen supply solvent is 1:0.03:1, the temperature of the mixed reaction raw materials is 380 ℃, then carrying out hydro-thermal cracking reaction in a fully mixed suspension bed reactor, the temperature of the hydro-thermal cracking reaction is 450 ℃, the pressure of the hydro-thermal cracking reaction is 20MPaG, hydrogen is introduced into each stage of fully mixed suspension bed reactor, the volume ratio of total hydrogen to oil is 1000:1, and a hydrogenation product is obtained after the reaction;
the preparation method comprises the following steps of preparing a hydrogen donor solvent by adopting a fixed bed hydrogenation reactor, wherein the active component of the used catalyst is Co, the reaction temperature of the preparation of the hydrogen donor solvent is 300 ℃, and the reaction pressure is 13 MPaG;
(2) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1), wherein the gas-liquid separation adopts a step separation mode and comprises hot high-pressure separation, warm high-pressure separation, cold high-pressure separation, hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, wherein the hot high-pressure separation product is divided into two parts, one part is sequentially subjected to warm high-pressure separation and cold high-pressure separation, the other part is sequentially subjected to hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, the operation temperature of the hot high-pressure separation is 380 ℃, the operation temperature of the warm high-pressure separation is 270 ℃, the operation temperature of the cold high-pressure separation is 45 ℃, the high-pressure operation pressure is 20MPa, the operation temperature of the hot medium-pressure separation is 380 ℃, the operation temperature of the warm medium-pressure separation is 210 ℃, the medium-pressure operation pressure is 4.5MPa, the operation temperature of the cold low-pressure separation is 45 ℃, and the operation pressure is 2.5MPa, gas obtained by gas-liquid separation is compressed and then returns to the step (1) for reuse;
and (2) the liquid-liquid separation is completed by adopting a reduced pressure distillation mode and sequentially passing through a stabilizing tower and a reduced pressure tower, wherein the operating pressure of the stabilizing tower is 0.4MPa, the operating pressure of the reduced pressure tower is 15kPa, the operating temperature is 200 ℃, a light oil product, circulating oil and solid-containing unconverted oil are obtained, the circulating oil returns to the step (1) for reaction again, and the weight ratio of the returned circulating oil to the heavy inferior oil in the step (1) is 0.3: 1.
In the embodiment, the method is adopted to carry out hydrogenation and lightening of the heavy inferior oil, the conversion rate of the heavy inferior oil can reach 96%, and the yield of the light oil product can reach 92%.
Example 5:
the embodiment provides a hydro-thermal cracking method for heavy inferior oil, which is carried out by adopting the device in the embodiment 1 and comprises the following steps:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen supply solvent, wherein the heavy inferior oil is coal tar heavy distillate, the active components of the catalyst are Co and Ni, the hydrogen supply solvent is bicyclic aromatic solvent oil, the hydrogen supply index of the heavy inferior oil is 30, the weight ratio of the heavy inferior oil to the catalyst to the hydrogen supply solvent is 1:0.01:0.5, the temperature of the mixed reaction raw materials is 350 ℃, then carrying out the hydro-thermal cracking reaction in a fully mixed suspension bed reactor, the temperature of the hydro-thermal cracking reaction is 420 ℃, the pressure of the hydro-thermal cracking reaction is 15MPaG, hydrogen is introduced into each stage of fully mixed suspension bed reactor, the volume ratio of the total hydrogen to the oil is 1500:1, and a hydrogenation product is obtained after the reaction;
the hydrogen donor solvent is prepared by adopting a fixed bed hydrogenation reactor, the active component of the used catalyst is Ni, the reaction temperature for preparing the hydrogen donor solvent is 220 ℃, and the reaction pressure is 16 MPaG;
(2) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1), wherein the gas-liquid separation adopts a step separation mode and comprises hot high-pressure separation, warm high-pressure separation, cold high-pressure separation, hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, the hot high-pressure separation product is divided into two parts, one part is sequentially subjected to the warm high-pressure separation and the cold high-pressure separation, the other part is sequentially subjected to the hot medium-pressure separation, the warm medium-pressure separation and the cold low-pressure separation, the operation temperature of the hot high-pressure separation is 350 ℃, the operation temperature of the warm high-pressure separation is 250 ℃, the operation temperature of the cold high-pressure separation is 40 ℃, the high-pressure operation pressure is 25MPa, the operation temperature of the hot medium-pressure separation is 320 ℃, the operation temperature of the warm medium-pressure separation is 180 ℃, the medium-pressure operation pressure is 6.0MPa, the operation temperature of the cold low-pressure separation is 40 ℃, and the operation pressure is 3.0MPa, gas obtained by gas-liquid separation is compressed and then returns to the step (1) for reuse;
and (2) the liquid-liquid separation is completed by adopting a reduced pressure distillation mode and sequentially passing through a stabilizing tower and a reduced pressure tower, wherein the operating pressure of the stabilizing tower is 0.2MPa, the operating pressure of the reduced pressure tower is 5kPa, the operating temperature is 350 ℃, a light oil product, circulating oil and solid-containing unconverted oil are obtained, the circulating oil returns to the step (1) for reaction again, and the weight ratio of the returned circulating oil to the heavy inferior oil in the step (1) is 0.5: 1.
In the embodiment, the method is adopted for carrying out hydrogenation and lightening on the heavy inferior oil, the conversion rate of the heavy inferior oil can reach 95.5%, and the yield of the light oil product can reach 92.5%.
Example 6:
the embodiment provides a hydro-thermal cracking method for heavy inferior oil, which is carried out by adopting the device in the embodiment 1 and comprises the following steps:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen supply solvent, wherein the heavy inferior oil is shale oil-based heavy oil fraction, the active component of the catalyst is Mo, the hydrogen supply solvent is polycyclic aromatic hydrocarbon solvent oil, the hydrogen supply index of the heavy inferior oil is 21, the weight ratio of the heavy inferior oil to the catalyst to the hydrogen supply solvent is 1:0.05:1.5, the temperature of the mixed reaction raw materials is 420 ℃, then carrying out the hydro-thermal cracking reaction in a fully mixed suspension bed reactor, the temperature of the hydro-thermal cracking reaction is 480 ℃, the pressure of the hydro-thermal cracking reaction is 25MPaG, hydrogen is introduced into each stage of fully mixed suspension bed reactor, the volume ratio of the total hydrogen to the oil is 500:1, and a hydrogenation product is obtained after the reaction;
the hydrogen donor solvent is prepared by adopting a fixed bed hydrogenation reactor, the active component of the used catalyst is Mo, the reaction temperature for preparing the hydrogen donor solvent is 380 ℃, and the reaction pressure is 10 MPaG;
(2) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1), wherein the gas-liquid separation adopts a step separation mode and comprises hot high-pressure separation, warm high-pressure separation, cold high-pressure separation, hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, wherein the hot high-pressure separation product is divided into two parts, one part is sequentially subjected to the warm high-pressure separation and the cold high-pressure separation, the other part is sequentially subjected to the hot medium-pressure separation, the warm medium-pressure separation and the cold low-pressure separation, the operation temperature of the hot high-pressure separation is 420 ℃, the operation temperature of the warm high-pressure separation is 280 ℃, the operation temperature of the cold high-pressure separation is 50 ℃, the high-pressure operation pressure is 16MPa, the operation temperature of the hot medium-pressure separation is 410 ℃, the operation temperature of the warm medium-pressure separation is 250 ℃, the medium-pressure operation pressure is 3.0MPa, the operation temperature of the cold low-pressure separation is 50 ℃, and the operation pressure is 2.0MPa, gas obtained by gas-liquid separation is compressed and then returns to the step (1) for reuse;
and (2) the liquid-liquid separation is completed by adopting a reduced pressure distillation mode and sequentially passing through a stabilizing tower and a reduced pressure tower, wherein the operating pressure of the stabilizing tower is 0.6MPa, the operating pressure of the reduced pressure tower is 25kPa, the operating temperature is 80 ℃, a light oil product, circulating oil and solid-containing unconverted oil are obtained, the circulating oil returns to the step (1) for reaction again, and the weight ratio of the returned circulating oil to the heavy inferior oil in the step (1) is 0.2: 1.
In the embodiment, the method is adopted to carry out hydrogenation and lightening of the heavy inferior oil, the conversion rate of the heavy inferior oil can reach 96.5%, and the yield of the light oil product can reach 93%.
Example 7:
the embodiment provides a hydro-thermal cracking method for heavy inferior oil, which is implemented by adopting the device in the embodiment 3 and comprises the following steps:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen supply solvent, introducing the mixture into a fully mixed suspension bed reactor to perform a hydro-thermal cracking reaction, wherein the heavy inferior oil is a heavy oil fraction containing solid coke breeze, the active components of the catalyst are Fe and Co, the hydrogen supply solvent is bicyclic aromatic hydrocarbon solvent oil, the hydrogen supply index of the bicyclic aromatic hydrocarbon solvent oil is 27, the weight ratio of the heavy inferior oil to the catalyst to the hydrogen supply solvent is 1:0.02:1.2, the temperature of the mixed reaction raw material is 400 ℃, the temperature of the hydro-thermal cracking reaction is 465 ℃, the pressure of the hydro-thermal cracking reaction is 22MPaG, the hydrogen is introduced into each stage of fully mixed suspension bed reactor, the volume ratio of the total hydrogen to the oil is 1200:1, and obtaining a hydrogenation product after the reaction;
the hydrogen donor solvent is prepared by adopting a fixed bed hydrogenation reactor, the active component of the catalyst is Ni, the reaction temperature for preparing the hydrogen donor solvent is 350 ℃, and the reaction pressure is 12 MPaG;
step (2) the method in example 4 was referred to.
In the embodiment, the method is adopted for carrying out hydrogenation and lightening on the heavy inferior oil, the conversion rate of the heavy inferior oil can reach 95.8%, and the yield of the light oil product can reach 92.6%.
Example 8:
the embodiment provides a hydro-thermal cracking method for heavy inferior oil, which is implemented by adopting the device in the embodiment 2 and comprises the following steps:
step (1) the method of example 4 was referred to;
(2) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1), wherein the gas-liquid separation adopts a step separation mode and comprises hot high-pressure separation, warm high-pressure separation, cold high-pressure separation, hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, wherein the hot high-pressure separation product is divided into two parts, one part is sequentially subjected to the warm high-pressure separation and the cold high-pressure separation, the other part is sequentially subjected to the hot medium-pressure separation, the warm medium-pressure separation and the cold low-pressure separation, the operation temperature of the hot high-pressure separation is 400 ℃, the operation temperature of the warm high-pressure separation is 260 ℃, the operation temperature of the cold high-pressure separation is 48 ℃, the high-pressure operation pressure is 18MPa, the operation temperature of the hot medium-pressure separation is 350 ℃, the operation temperature of the warm medium-pressure separation is 225 ℃, the medium-pressure operation pressure is 5.0MPa, the operation temperature of the cold low-pressure separation is 42 ℃, and the operation pressure is 2.5MPa, returning the gas obtained by gas-liquid separation to the step (1) for reuse;
and (2) the liquid-liquid separation is completed by adopting a reduced pressure distillation mode and sequentially passing through a stabilizing tower and a reduced pressure tower, wherein the operating pressure of the stabilizing tower is 0.5MPa, the operating pressure of the reduced pressure tower is 20kPa, the operating temperature is 300 ℃, a light oil product, circulating oil and solid-containing unconverted oil are obtained, the circulating oil returns to the step (1) for reaction again, and the weight ratio of the returned circulating oil to the heavy inferior oil in the step (1) is 0.4: 1.
In the embodiment, the method is adopted for carrying out hydrogenation and lightening on the heavy inferior oil, the conversion rate of the heavy inferior oil can reach 96.2%, and the yield of the light oil product can reach 92.3%.
Comparative example 1:
this comparative example provides an apparatus and process for the hydrocracking of heavy, poor quality oil, with reference to the apparatus of example 1, except that: the inlet of the hydrocracking reaction unit 2 is not connected with a hydrogen supply solvent feeding pipeline, and the side draw-out port of the product separation unit 4 is not connected with the hydrocracking reaction unit 2.
The process is referred to the process in example 4, with the only difference that: the raw material in the step (1) does not contain a hydrogen donor solvent; and (3) the circulating oil in the step (2) is not returned to the step (1) for use.
In the comparative example, the impurity content in the heavy inferior oil is high, a hydrogen supply solvent is not used, the dispersity of hydrogen is weak, coking reaction is easy to occur, the conversion rate of the heavy inferior oil is reduced to 90%, and the yield of the light oil product is only 85%; meanwhile, the reactor is easy to block due to coking reaction, and the catalyst is easy to inactivate, so that the long-time stable operation of the device cannot be ensured.
It can be seen from the above examples and comparative examples that the apparatus of the present invention uses the reaction unit and the separation unit as main bodies, and adopts the suspension bed reactor to realize the hydrogenation and lightening of heavy and poor oil, and uses the hydrogen supply solvent as the auxiliary reaction raw material, which can effectively inhibit the coking reaction, and then uses the high-low pressure separation and product separation unit to fully separate and recycle the reaction product, so as to integrally improve the conversion rate of the heavy and poor oil and the yield of the light oil product, wherein the conversion rate of the former reaches more than 95%, and the yield of the latter reaches more than 92%; the device has the advantages of simple structure, simple process route and low coking tendency, is favorable for realizing long-period stable operation of the device, reduces the production cost and improves the production efficiency.
The applicant states that the present invention is illustrated by the detailed apparatus and method of the present invention through the above embodiments, but the present invention is not limited to the above detailed apparatus and method, i.e. it is not meant to imply that the present invention must be implemented by the above detailed apparatus and method. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the means for substitution and addition of means for carrying out the invention, selection of specific means, etc., are within the scope and disclosure of the invention.
Claims (10)
1. The device is characterized by comprising a hydro-thermal cracking reaction unit, a high-low pressure separation unit and a product separation unit, wherein the hydro-thermal cracking reaction unit comprises at least one stage of fully-mixed suspended bed reactor, an inlet of the hydro-thermal cracking reaction unit is connected with a hydrogen supply solvent feeding pipeline, an outlet at the top of the hydro-thermal cracking reaction unit is connected with an inlet of the high-low pressure separation unit, a liquid phase outlet of the high-low pressure separation unit is connected with an inlet of the product separation unit, and a side draw outlet of the product separation unit is connected with an inlet of the hydro-thermal cracking reaction unit.
2. The device according to claim 1, wherein the number of stages of the fully mixed suspended bed reactor is 1-3;
preferably, the top outlet of the previous stage of fully mixed type suspended bed reactor is connected with the bottom inlet of the next stage of fully mixed type suspended bed reactor;
preferably, the bottom of each stage of the fully mixed type suspended bed reactor is provided with a circulating loop;
preferably, the circulating loops are provided with circulating pumps.
3. The device according to claim 1 or 2, wherein the high-low pressure separation unit comprises a hot high-pressure separator, a warm high-pressure separator, a cold high-pressure separator, a hot medium-pressure separator, a warm medium-pressure separator and a cold low-pressure separator, the separators in the high-low pressure separation unit are divided into two branches, the upper outlet of the hot high-pressure separator is sequentially connected with the warm high-pressure separator and the cold high-pressure separator, and the lower outlet of the hot high-pressure separator is sequentially connected with the hot medium-pressure separator, the warm medium-pressure separator and the cold low-pressure separator;
preferably, the lower outlet of the warm high-pressure separator and the upper outlet of the hot medium-pressure separator are both connected to the inlet of the warm medium-pressure separator, the upper outlet of the cold high-pressure separator is connected to the hydro-thermal cracking reaction unit, the lower outlet of the cold high-pressure separator is connected to the inlet of the cold low-pressure separator, and the lower outlets of the hot medium-pressure separator, the warm medium-pressure separator and the cold low-pressure separator are all connected to the product separation unit;
preferably, the apparatus further comprises a hydrogen compression unit disposed on the circulation line of the separation gas of the high-and low-pressure separation unit.
4. The apparatus according to any one of claims 1 to 3, wherein the product separation unit comprises a stabilizer and a vacuum tower which are connected in sequence, wherein a top outlet of the vacuum tower produces light oil products, a side outlet of the vacuum tower produces circulating oil, and a bottom outlet of the vacuum tower produces solid unconverted oil;
preferably, the device also comprises a mixed feeding unit, wherein the outlet of the mixed feeding unit is connected with the inlet of the hydrocracking reaction unit;
preferably, the hydrogen supply solvent feeding pipeline, the circulating pipeline of the high-low pressure separation unit and the circulating pipeline of the product separation unit are all connected to the mixed feeding unit.
5. A process for the hydrocracking of heavy and poor oils using the apparatus of any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) mixing heavy inferior oil, hydrogen, a catalyst and a hydrogen donor solvent, and then carrying out a hydro-thermal cracking reaction to obtain a hydrogenation product;
(2) and (3) sequentially carrying out gas-liquid separation and liquid-liquid separation on the hydrogenation product obtained in the step (1) to obtain a light oil product and circulating oil, and returning the circulating oil to the step (1) for reaction again.
6. The method according to claim 5, wherein the heavy inferior oil of step (1) comprises any one of vacuum residue, coal tar heavy fraction, shale oil base heavy oil fraction, heavy oil fraction containing solid coke breeze or heavy oil fraction blended with pulverized coal or a combination of at least two of the above;
preferably, the active component of the catalyst in the step (1) comprises any one or a combination of at least two of Fe, Co, Ni or Mo;
preferably, the hydrogen donor solvent in the step (1) comprises any one of alkane solvent oil, bicyclic aromatic solvent oil or polycyclic aromatic solvent oil or the combination of at least two of the alkane solvent oil, bicyclic aromatic solvent oil and polycyclic aromatic solvent oil;
preferably, the hydrogen donating solvent of step (1) has a hydrogen donating index of not less than 20;
preferably, the weight ratio of the heavy inferior oil, the catalyst and the hydrogen donor solvent in the step (1) is 1 (0.01-0.05) to (0.3-1.5).
7. The method according to claim 5 or 6, wherein the hydrogen donor solvent of step (1) is prepared using a fixed bed hydrogenation reactor;
preferably, the hydrogen donor solvent is prepared by shallow hydrogenation of distillate oil of 250-420 ℃ of petroleum, coal tar or shale oil;
preferably, the active component of the catalyst used for the preparation of the hydrogen donor solvent comprises any one or a combination of at least two of Co, Ni or Mo;
preferably, the reaction temperature for preparing the hydrogen donor solvent is 220-380 ℃;
preferably, the reaction pressure for preparing the hydrogen donor solvent is 10-16 MPaG.
8. The method according to any one of claims 5 to 7, wherein the temperature of the mixed reaction raw materials in the step (1) is 350 to 420 ℃;
preferably, the hydrocracked reaction in step (1) is carried out in at least one stage of fully mixed suspension bed reactor;
preferably, the hydrogen is introduced into each stage of fully mixed suspension bed reactor;
preferably, the temperature of the hydro-thermal cracking reaction in the step (1) is 420-480 ℃;
preferably, the pressure of the hydro-thermal cracking reaction in the step (1) is 15-25 MPaG;
preferably, the volume ratio of the total hydrogen to oil in the hydro-thermal cracking reaction in the step (1) is (500-1500): 1.
9. The method according to any one of claims 5 to 8, wherein the gas-liquid separation in step (2) adopts a step separation mode, comprising hot high-pressure separation, warm high-pressure separation, cold high-pressure separation, hot medium-pressure separation, warm medium-pressure separation and cold low-pressure separation, wherein the product of the hot high-pressure separation is divided into two parts, one part is sequentially subjected to the warm high-pressure separation and the cold high-pressure separation, and the other part is sequentially subjected to the warm medium-pressure separation, the warm medium-pressure separation and the cold low-pressure separation;
preferably, the operation temperature of the hot high-pressure separation is 350-420 ℃, the operation temperature of the warm high-pressure separation is 250-280 ℃, and the operation temperature of the cold high-pressure separation is 40-50 ℃;
preferably, the operation pressure of the hot high-pressure separation, the warm high-pressure separation and the cold high-pressure separation is 16-25 MPa;
preferably, the operation temperature of the hot medium-pressure separation is 320-410 ℃, and the operation pressure is 3.0-6.0 MPa;
preferably, the operation temperature of the medium-temperature and medium-pressure separation is 180-250 ℃, and the operation pressure is 3.0-6.0 MPa;
preferably, the operation temperature of the cold low-pressure separation is 40-50 ℃, and the operation pressure is 2.0-3.0 MPa;
preferably, the gas obtained by gas-liquid separation is compressed and then returned to the step (1) for reuse.
10. The method according to any one of claims 5 to 9, wherein the liquid-liquid separation of step (2) comprises: separating by adopting a reduced pressure distillation mode;
preferably, the decompression process is completed through a stabilizing tower and a decompression tower in sequence, the operating pressure of the stabilizing tower is 0.2-0.6 MPa, and the operating pressure of the decompression tower is 5-25 kPa;
preferably, the reduced pressure distillation is mainly carried out in a reduced pressure tower, and the operating temperature is 50-360 ℃;
preferably, the product of the liquid-liquid separation in step (2) further comprises solid-containing unconverted oil;
preferably, the weight ratio of the circulating oil returned after the liquid-liquid separation in the step (2) to the heavy inferior oil in the step (1) is (0.2-0.5): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110630598.2A CN113234475A (en) | 2021-06-07 | 2021-06-07 | Heavy inferior oil hydro-thermal cracking device and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110630598.2A CN113234475A (en) | 2021-06-07 | 2021-06-07 | Heavy inferior oil hydro-thermal cracking device and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113234475A true CN113234475A (en) | 2021-08-10 |
Family
ID=77136990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110630598.2A Pending CN113234475A (en) | 2021-06-07 | 2021-06-07 | Heavy inferior oil hydro-thermal cracking device and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234475A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277878A (en) * | 2013-07-05 | 2015-01-14 | 任相坤 | Two-stage slurry bed hydrogenation process of high temperature coal tar |
| CN106635159A (en) * | 2016-12-06 | 2017-05-10 | 胜帮科技股份有限公司 | High solid content coal tar suspended bed hydrogenation system and technology |
| CN109181762A (en) * | 2018-10-17 | 2019-01-11 | 胜帮科技股份有限公司 | A kind of multistage suspension bed hydroprocessing device and method of poor oil |
| CN110257102A (en) * | 2019-07-17 | 2019-09-20 | 胜帮科技股份有限公司 | A kind of raw material classification rich in polycyclic aromatic hydrocarbon faces hydrogen pyrolysis and produces the production system and method for light aromatics |
| CN110643391A (en) * | 2019-09-02 | 2020-01-03 | 中科合成油技术有限公司 | Method for converting coal tar/heavy oil into liquefied gas, naphtha and diesel oil |
-
2021
- 2021-06-07 CN CN202110630598.2A patent/CN113234475A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277878A (en) * | 2013-07-05 | 2015-01-14 | 任相坤 | Two-stage slurry bed hydrogenation process of high temperature coal tar |
| CN106635159A (en) * | 2016-12-06 | 2017-05-10 | 胜帮科技股份有限公司 | High solid content coal tar suspended bed hydrogenation system and technology |
| CN109181762A (en) * | 2018-10-17 | 2019-01-11 | 胜帮科技股份有限公司 | A kind of multistage suspension bed hydroprocessing device and method of poor oil |
| CN110257102A (en) * | 2019-07-17 | 2019-09-20 | 胜帮科技股份有限公司 | A kind of raw material classification rich in polycyclic aromatic hydrocarbon faces hydrogen pyrolysis and produces the production system and method for light aromatics |
| CN110643391A (en) * | 2019-09-02 | 2020-01-03 | 中科合成油技术有限公司 | Method for converting coal tar/heavy oil into liquefied gas, naphtha and diesel oil |
Non-Patent Citations (2)
| Title |
|---|
| 于江林等: "《石油化工-过程装备与控制》", 31 May 2008, 哈尔滨工业大学出版社 * |
| 郑发元: "《煤焦油加氢技术》", 31 July 2016, 东北师范大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1783194B1 (en) | A process for direct liquefaction of coal | |
| CN102115674B (en) | Coal liquefaction and petroleum refining combined method | |
| CN102517071B (en) | Method for mixing and processing wash oil and direct coal liquefaction oil | |
| CN105462610B (en) | A kind of anthracene oil hydrogenation method | |
| CN105567321A (en) | Method for producing oil product by corefining coal and oil | |
| CN106433775A (en) | Coal and oil coprocessing method and device | |
| CN106906001B (en) | Method for co-processing coal with high content of inert components and heavy oil | |
| CN107267186A (en) | The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon | |
| CN105925304B (en) | DCL/Direct coal liquefaction cycle solvent and preparation method thereof | |
| CN108048121B (en) | Direct coal liquefaction method and direct coal liquefaction device | |
| CN105713662A (en) | Hydrotreating and catalytic cracking combined process | |
| CN109355100B (en) | Coal tar processing and coal co-refining combined process | |
| CN103540359B (en) | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline | |
| CN113234475A (en) | Heavy inferior oil hydro-thermal cracking device and method | |
| EP3533856B1 (en) | Method for preparing hexadecahydropyrene | |
| CN106635160B (en) | A kind of coal and coal tar mixed hydrogenation system and technique | |
| CN108865253A (en) | The method of coal Direct Hydrogenation liquefaction richness production aromatic hydrocarbons | |
| CN109181762B (en) | Multistage suspension bed hydrogenation device and method for inferior oil | |
| CN110551515B (en) | Device and method for preparing aromatic hydrocarbon through coal staged hydropyrolysis | |
| CN106967458A (en) | A kind of joint catalyst cracking method for handling residual oil and extra heavy oil | |
| CN104277878B (en) | A kind of two-stage slurry state bed hydroprocessing technique of high temperature coal-tar | |
| CN109777488B (en) | Refinery gas combined processing technology | |
| CN108504378B (en) | Preparation method of coal hydropyrolysis hydrogen-donating solvent oil, hydrogen-donating solvent oil prepared by same and application thereof | |
| CN115491221B (en) | Solvent for coal hydrogenation liquefaction and coal hydrogenation liquefaction method | |
| CN112980504B (en) | Process and device for preparing oil product by mixing oil slurry, recycle oil and coking wax 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210810 |