CN116410781A - Method for producing ethylene raw material by diesel hydrocracking - Google Patents
Method for producing ethylene raw material by diesel hydrocracking Download PDFInfo
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- CN116410781A CN116410781A CN202111643492.2A CN202111643492A CN116410781A CN 116410781 A CN116410781 A CN 116410781A CN 202111643492 A CN202111643492 A CN 202111643492A CN 116410781 A CN116410781 A CN 116410781A
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 78
- 239000002994 raw material Substances 0.000 title claims abstract description 53
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005977 Ethylene Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 85
- 238000005336 cracking Methods 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000007670 refining Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005194 fractionation Methods 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000012188 paraffin wax Substances 0.000 description 30
- 239000002283 diesel fuel Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005671 trienes Chemical class 0.000 description 3
- 238000004148 unit process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (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 discloses a method for producing ethylene raw material by diesel hydrocracking, which is characterized by comprising the following steps: (a) Mixing the diesel raw material with hydrogen, and carrying out hydrofining and hydrocracking; (b) After gas-liquid separation, steam stripping and fractionation, the hydrogenation mixture flow produced in the step (a) is respectively provided with a first distillation section, a second distillation section, a third distillation section and a fourth distillation section; the distillation range of the first distillation section is not more than 100 ℃, the final distillation point of the second distillation section is not more than 180 ℃, the final distillation point of the third distillation section is not more than 250 ℃, and the distillation range is preferably 180-250 ℃; (c) And (3) fully refining the generated third fraction to hydrofining or feeding the third fraction to a hydrocracking reaction unit for recycling processing. Compared with the traditional hydrocracking method for producing naphtha, ethylene cracking raw materials and partial aviation kerosene by straight-run diesel, the method has obvious advantages in the aspects of oil conversion, ethylene cracking raw material quality and ethylene yield.
Description
Technical Field
The invention belongs to the field of petroleum refining, and particularly relates to a method for producing ethylene raw materials by diesel hydrocracking.
Background
With the gradual improvement of the oil refining capability of China, the relatively low cost of the whole economy and the gradual improvement of new energy and sustainable development energy in the whole energy structure, the requirements of China on traditional gasoline and diesel clean fuels are gradually slowed down, and particularly the requirements of diesel are increased negatively. Taking the structure of the refinery product as an example, the yield of the light oil product is 50-60%, and the enterprises integrating the refining and the integration can approach 35-40%. The high yield characteristic of the light oil product promotes the current enterprises to carry out the secondary conversion of gasoline, diesel oil and aviation kerosene. At present, the demands of chemical raw materials are vigorous, and the demands of ethylene and propylene are rapidly increased, so that the technology for maximizing the yield of the ethylene material and producing other clean oil products is particularly important.
From the standpoint of the steam-cracked feedstock, suitable steam-cracked feedstocks include conventional straight run naphtha, light naphtha, ethane, hydrocracked tail oil, and the like. The main routes for ethylene production are therefore: (1) The technical route for producing chemical raw materials by wax oil hydrocracking can ensure that the oriented conversion of vacuum wax oil fraction can produce high-quality raw materials suitable for ethylene cracking by introducing a catalyst with suitable activity and selective ring opening, and has a BMCI value of no more than 12 and high paraffin content. (2) The technological route of diesel oil solvent extraction dearomatization reduces naphthenes and most aromatic hydrocarbons in straight-run diesel oil through the effect of polar separation, improves the paraffin content in raffinate oil, and realizes the substantial reduction of diesel oil BMCI value. (3) The diesel hydrocracking process realizes aromatic saturation and naphthene ring opening in diesel, and ensures that low BMCI value components are largely reserved, but diesel hydrocracking and wax oil hydrocracking are slower in reaction rate than wax oil hydrocracking reaction rate due to the difference of raw materials and the difference of reaction processes, and a large amount of gas components are easily generated in diesel hydrocracking.
The production of ethylene by diesel hydrocracking is also reported, mainly using a flexible catalyst and a high-medium oil catalyst, ensuring the conversion rate and the yield, and simultaneously realizing the high paraffin content and the low aromatic hydrocarbon content of unconverted tail oil by adjusting the activity of the catalyst, and ensuring the maximization production of ethylene cracking raw materials with low BMCI value by both density and distillation range.
Because the raw materials in the hydrocracking reaction process of the diesel are mainly concentrated in the range of 180-350 ℃, the carbon number molecules are smaller, the current diesel hydrogenation conversion pressure level is low, the conversion of most aromatic hydrocarbon and naphthene cannot be realized, and the matched process and catalyst are required to cooperate to realize the production of the ethylene cracking raw material with low BMCI value by the mixed diesel.
Liu Jianwei et al (petroleum refining and chemical industry, 2020, 51 (9): 34-40) report that when straight-run diesel is processed by a conventional hydrocracking process with a single-stage dual-agent tandem hydrocracking, the BMCI value of the unconverted oil fraction > 180 ℃ is reduced to 18.8 under the condition of controlling the naphtha yield to 10%, but the diesel fraction still contains a large amount of naphthenes (30-40 wt%) and the relative paraffin content is increased by 5-8 percentage points. Although capable of meeting ethylene feed requirements, such high BMCI triene yields still have a gap from other readily cleavable components.
CN1955261a discloses a poor quality catalytic cracking diesel hydrocracking method. The method mixes poor quality catalytic diesel with heavy hydrocracking raw materials, carries out hydrocracking first, and carries out secondary hydrocracking on the obtained middle distillate oil to obtain high aromatic heavy naphtha and tail oil with low BMCI value. The middle distillate oil obtained in one step has no sulfur, nitrogen and other impurities, and the catalyst activity is fully utilized, so that the catalyst can be operated at a higher space velocity and a lower temperature, and even at a lower hydrogen partial pressure, and the economy is improved. And the lower hydrogen partial pressure is beneficial to converting middle distillate into heavy naphtha with high aromatic potential, and the lower temperature reduces the further cracking of the heavy naphtha, thereby greatly improving the yield of the heavy naphtha. The process is mainly described for catalytic cracking diesel conversion and middle distillate processing, but is not presented and described for how to maximize ethylene production for straight-run diesel hydroconversion.
CN103773487a discloses a hydrocracking method for catalytically cracking diesel, wherein a mixture of diesel raw materials and hydrogen is contacted and reacted with a hydrofining catalyst in a hydrofining reactor, the liquid effluent of the hydrofining reactor is not separated, enters the hydrocracking reactor to be contacted and reacted with the hydrocracking catalyst, the reaction effluent of the hydrocracking reactor is separated and fractionated to obtain hydrogen-rich gas, light naphtha fraction, gasoline fraction, recycle fraction and diesel fraction, the distillation range of the recycle fraction is 190-300 ℃, and the recycle fraction is returned to the inlet of the hydrocracking reactor. The method provided by the invention improves the hydrocarbon composition of the feed of the hydrocracking reaction zone, and can effectively improve the yield and octane number of the gasoline fraction. However, this method is a method of recycling, but is not reported to be suitable for producing ethylene from straight-run diesel.
The CN10942336A patent discloses a hydrocracking method for processing straight-run diesel oil, and the invention discloses a hydrocracking method which comprises the following steps: (1) Mixing the diesel raw material with hydrogen, and carrying out desulfurization, denitrification and arene saturation reaction in a hydrofining reactor; (2) The effluent from the step (1) enters a hydrocracking reactor, the hydrocracking reactor comprises at least two catalyst beds, the content of the molecular sieve of the hydrocracking catalyst containing the modified Y molecular sieve in each catalyst bed increases gradually along the direction of the material flow, and the average pore diameter of the catalyst decreases gradually; (3) The effluent of the hydrocracking reactor is separated into gas phase and liquid phase, the gas phase is recycled, the liquid phase enters a fractionating tower, and naphtha, aviation kerosene, diesel oil and tail oil are obtained through fractionation. The method takes diesel oil as raw material, increases the yield of heavy naphtha with high aromatic potential through reasonable combination of hydrocracking catalysts with different functions, and improves the quality of aviation kerosene and diesel oil products. Although this patent discloses how diesel is converted, there is no report on how the process for producing ethylene cracking feed is optimized.
In the diesel conversion process, in order to further increase the triene yield which can be used for ethylene cracking raw material, the target product yield of unconverted oil can be increased by increasing the conversion rate, but for diesel fraction, as the conversion rate increases, although the relative content of unconverted paraffin increases, a large amount of dry gas and liquefied gas fraction is produced, further increasing the hydrogen consumption and simultaneously leading to the decrease of the absolute content of paraffin. If the unconverted diesel recycling process is adopted, the paraffin content of the unconverted oil is reduced. Meanwhile, in the diesel conversion process, due to the difference and selectivity of the catalyst on paraffin/naphthene conversion capability, the relative content of paraffin tends to increase along with the increase of boiling point in the target product diesel, for example: in unconverted oil which is hydroconverted by using normal three fractions as raw materials, the fraction below 250 ℃ has relatively less paraffin content, 10-30wt% paraffin content, 60-80wt% naphthene content and the fraction above 250 ℃ has about 60-85wt% paraffin content. Thus, for the variability of paraffin content with the distillation range profile, it is necessary to reconsider the processing scheme in the diesel conversion process.
Disclosure of Invention
The invention aims to provide a method for producing ethylene raw materials by diesel hydrocracking, which solves the problems that BMCI values in diesel hydrocracking unconverted diesel are unevenly distributed along with distillation ranges, the BMCI value of the diesel is limited in improvement range under the condition of lower conversion rate, and the paraffin content in the hydrocracking unconverted diesel is relatively low in the prior art.
A process for producing an ethylene feedstock by diesel hydrocracking, comprising the steps of:
(a) Mixing the diesel raw material with hydrogen, and carrying out hydrofining and hydrocracking;
(b) After gas-liquid separation, steam stripping and fractionation, the hydrogenation mixture flow produced in the step (a) is respectively provided with a first distillation section, a second distillation section, a third distillation section and a fourth distillation section; the distillation range of the first distillation section is not more than 100 ℃, the final distillation point of the second distillation section is not more than 180 ℃, the final distillation point of the third distillation section is not more than 250 ℃, and the distillation range is preferably 180-250 ℃; wherein the ethylene cracking feed comprises a first fraction having a paraffin content of less than 60 wt.% and a fourth fraction having a paraffin content of less than 60 wt.% which are optionally used as ethylene cracking feed.
(c) And (3) fully refining the generated third fraction to hydrofining or feeding the third fraction to a hydrocracking reaction unit for recycling processing.
The invention relates to a method for producing ethylene raw material by diesel hydrocracking, wherein the diesel raw material is straight-run diesel and/or coked diesel.
The invention relates to a method for producing ethylene raw material by diesel hydrocracking, which comprises the following steps: the reaction pressure is 6-15Mpa, preferably 6-10Mpa, the reaction temperature is 330-380 ℃, preferably 330-370 ℃, and the hydrocracking process conditions are as follows: the reaction pressure is 6-15Mpa, preferably 6-10Mpa, the reaction temperature is 330-390 ℃, preferably 345-370 ℃, and the reaction space velocity of refining and cracking is 0.5-3.0h -1 The hydrogen oil volume ratio is 500-1500 v/v, preferably 500-1000v/v.
In the method for producing ethylene raw materials by diesel hydrocracking, in the step (c), the third distillation section can be recycled to the feeding of the hydrofining reactor or the feeding of the hydrocracking reactor, and the mass ratio of the hydrofining feeding or the hydrocracking feeding to the recycled third distillation section is 1:1-10:1, preferably 3:1-10:1.
The invention has the beneficial effects that:
compared with the traditional hydrocracking method for producing naphtha, ethylene cracking raw materials and partial aviation kerosene by straight-run diesel, the method has obvious advantages in the aspects of oil conversion, ethylene cracking raw material quality and ethylene yield.
According to the invention, the structure of a target product and the molecular structure in the process of a reaction unit are optimally regulated, so that the optimal design of the molecular composition of the target product is realized, on the basis of the recognition of the difference of the molecular structure of the diesel hydrocracking product on the basis of the one-pass/partial cycle/full cycle process of the traditional diesel hydrocracking, the directional conversion ring-opening of naphthenes is realized by selectively recycling the third fraction section rich in naphthenes to the hydrocracking/hydrofining reaction unit, the problems of poor paraffin conversion selectivity and the like caused by recycling the traditional heavy unconverted oil are avoided, the paraffin content in unconverted oil and ethylene cracking raw materials is reserved to the maximum extent, and the triene yield of the ethylene cracking raw materials is improved.
Drawings
FIG. 1 is a process flow diagram of the invention for producing ethylene feedstock by diesel hydrocracking;
FIG. 2 is another process flow diagram of the present invention for producing ethylene feedstock by diesel hydrocracking.
Wherein reference numerals are used to refer to
1a hydrofining reactor; 2 hydrofining stream; 3 a hydrocracking reactor; 4 hydrocracking stream; 5 a gas-liquid separator; 6a liquid stream; 7, a fractionating tower; 8 dry gas and liquefied gas streams; 9 a first distillation stage; 10 a second distillation stage; 11 a third distillation stage; 12 a fourth distillation stage; 13 diesel fuel raw material; 14 hydrogen; 15 ethylene cracker.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
As shown in fig. 1, a mixed stream obtained by mixing a diesel raw material 15 and hydrogen 16 enters a hydrofining reactor 1, a hydrofining stream 2 passing through an outlet of the hydrofining reactor 1 enters a hydrocracking reactor 3, a hydrocracking stream 4 flowing out of the outlet of the hydrocracking reactor enters a gas-liquid separator 5, a liquid stream 6 flowing out of the bottom outlet of the gas-liquid separator 5 enters a fractionating tower 7, and a hydrocracking product is obtained by passing through the fractionating tower 7, namely a dry gas and liquefied gas stream 8, a first fraction 9, a second fraction 10, a third fraction 11 and a fourth fraction 12, wherein the third fraction is recycled into the hydrofining reactor, or the first fraction and the fourth fraction can be used as ethylene cracking raw materials to enter an ethylene cracking device 15 as shown in fig. 2.
The raw materials used in the following examples are straight-run diesel or mixed diesel, and the basic properties are shown in Table 1.
Example 1
Straight-run diesel A was used as a raw material, and the properties of the raw material are shown in Table 1. The reaction pressure is 8Mpa through a hydrofining and hydrocracking reactor, and the refining and cracking airspeed are respectively 2.0h based on fresh materials -1 The hydrogen-oil ratio is 800, the refining temperature is 350 ℃, the cracking temperature is 345 ℃, the obtained full fraction product is cut and separated, the final distillation point of the first fraction 1A is 65 ℃, the final distillation point of the first fraction 1B is 92 ℃, the final distillation point of the second fraction is 180 ℃, the final distillation point of the third fraction is 250 ℃, the fraction is more than 250 ℃ and is the fourth fraction, wherein the fraction oil at 180-250 ℃ is recycled to the inlet of the cracking reactor, the fraction at 180-250 ℃ accounts for about 20wt% of fresh feeding proportion, the total yield of the first fraction 1B and the fourth fraction is 70wt%, the BMCI value of the fourth fraction is 12, the paraffin content is 65.2wt%, and the BMCI value of the first fraction 1B is 12.
Example 2
The straight-run diesel A is used as raw material, and is passed through hydrofining and hydrocracking unit reactor, pressure is 10Mpa, and refining and cracking airspeed are respectively 1.8h -1 The hydrogen-oil ratio is 1000, the refining temperature is 338 ℃, the cracking temperature is 358 ℃, the first fraction distillation range IBP-92 ℃, the second fraction distillation range 92-180 ℃, the third fraction distillation range 180-250 ℃, and the fourth fraction primary distillation point is more than 250 ℃. Wherein the 180-250 ℃ distillate oil is recycled to the inlet of the cracking reactor, the 180-250 ℃ distillate accounts for about 20wt% of the fresh feed proportion, the yield of the fourth fraction section (more than 250 ℃) is about 62wt%,>fraction BMCI at 250℃of about 12.4, paraffin content 63wt％。
Comparative example 1
The straight-run diesel A is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure is 8Mpa, and its refining and cracking airspeed are respectively 2.0h -1 The hydrogen-oil ratio is 800, the refining temperature is 350 ℃, the cracking temperature is 340 ℃, the first fraction distillation range IBP-65 ℃, the second fraction distillation range is 65-180 ℃, the third fraction primary distillation point is more than 180 ℃,>the fraction yield at 180℃was about 58.2wt%,>the BMCI of the 180℃fraction was about 13.98 and the paraffin content was 61.6% by weight.
Comparative example 2
The straight-run diesel A is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure grade is 8Mpa, hydrogen-oil ratio is 1000, and refining and cracking airspeed is 1.8 hr respectively -1 Refining temperature 358 ℃, cracking temperature 343 ℃, first fraction distillation range IBP-65 ℃, second fraction distillation range 65-180 ℃, third fraction primary distillation point > 180 ℃, wherein>The 180 ℃ distillate fraction was partially recycled to the inlet of the cracking reactor, the recycled material comprising about 20wt% of the fresh feed. The fraction yield at 180℃was about 50wt%,>the BMCI of the 180℃fraction was about 12.0 and the paraffin content was 63% by weight.
Example 3
The straight-run diesel oil B is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure is 8Mpa, hydrogen-oil ratio is 600, and the refining and cracking airspeed is 1.5 hr respectively -1 The refining temperature is 362 ℃, the cracking temperature is 363 ℃, the first fraction distillation range IBP-92 ℃, the second fraction distillation range 92-180 ℃, the third fraction distillation range 180-250 ℃, and the fourth fraction primary distillation point is more than 250 ℃. Wherein the distillate oil at 180-250 ℃ is recycled to the inlet of the cracking reactor, the distillate oil at 180-250 ℃ accounts for about 20wt% of the fresh feed,>the fraction yield at 250℃was about 82% by weight,>the BMCI of the 250℃fraction was about 13.5 and the paraffin content was 62.3% by weight.
Comparative example 3
The straight-run diesel oil B is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure is 8Mpa, hydrogen-oil ratio is 600, and the refining and cracking airspeed is 1.5 hr respectively -1 Refining temperature is 362 ℃, cracking temperature is 360 ℃, first fraction distillation range is IBP-65 ℃, second fraction distillation range is 65-18The initial point of the third fraction is more than 180 ℃,>the fraction yield at 180℃was about 85wt%,>the BMCI of the 180℃fraction was about 14.58 and the paraffin content was 59.7% by weight.
Comparative example 4
The straight-run diesel oil B is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure is 8Mpa, hydrogen-oil ratio is 600, and the refining and cracking airspeed is 1.5 hr respectively -1 The refining temperature is 362 ℃ and the cracking temperature is 363 ℃, wherein 30% of distillate oil at 180-250 ℃ is recycled to the inlet of a cracking reactor, the first distillate range IBP-92 ℃, the second distillate range IBP-180 ℃, the third distillate range 180-250 ℃ and the fourth distillate range primary distillation point is more than 250 ℃. The fraction at 180-250 ℃ accounts for about 10wt% of the fresh feed,>the fraction yield at 180℃was about 87wt%,>the BMCI of the 180℃fraction was about 15 and the paraffin content was 59% by weight.
Example 4
The straight-run diesel oil B is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure is 8Mpa, hydrogen-oil ratio is 500, and the refining and cracking airspeed is 1.5 hr respectively -1 The refining temperature is 363 ℃, the cracking temperature is 362 ℃, the first distillation range IBP-92 ℃, the second distillation range 92-180 ℃, the third distillation range 180-250 ℃ and the fourth distillation range primary distillation point is more than 250 ℃. Wherein the distillate oil at 180-250 ℃ is recycled to the inlet of the refining reactor, the distillate oil at 180-250 ℃ accounts for about 20wt% of the fresh feed,>the BMCI of the 250℃fraction was about 13.4 and the paraffin content was 62.1% by weight.
Example 5
Straight-run diesel oil B+10% coked diesel oil is used as raw material, and is passed through hydrofining and hydrocracking reactor, its pressure is 8Mpa, hydrogen-oil ratio is 550, and the refining and cracking airspeed is 1.5 hr respectively -1 Wherein the distillate oil at 180-250 ℃ is recycled to the inlet of the refining reactor, the distillation range IBP-92 ℃ in the first distillate section, the distillation range 92-180 ℃ in the second distillate section, the distillation range 180-250 ℃ in the third distillate section and the initial distillation point more than 250 ℃. The fraction at 180-250 ℃ accounts for about 20wt% of the fresh feed,>the BMCI of the 250℃fraction was about 13.2 and the paraffin content was 62.5 wt%.
Example 6
Takes straight-run diesel A as raw material, through addingThe hydrogen refining and hydrocracking unit process has pressure of 8MPa and refining and cracking airspeed of 2.0 hr based on fresh material -1 The refining temperature is 350 ℃, the cracking temperature is 342 ℃, the first fraction distillation range IBP-92 ℃, the second fraction distillation range 92-180 ℃, the third fraction distillation range 180-225 ℃ and the fourth fraction primary distillation point is more than 225 ℃. Wherein the fraction oil at 180-225 ℃ is partially recycled to the inlet of the refining reactor, and the fraction at 180-225 ℃ accounts for about 10wt% of the fresh feed>The BMCI value of the 225℃fraction was 13 and the paraffin content was 63% by weight.
Example 7
Straight-run diesel A was used as a raw material, and the properties of the raw material are shown in Table 1. Through the hydrofining and hydrocracking unit process, the pressure is 6Mpa, the hydrogen-oil ratio is 800, and the refining and cracking airspeed are respectively 2.0h based on fresh material -1 The refining temperature is 350 ℃, the cracking temperature is 350 ℃, the first fraction distillation range IBP-92 ℃, the second fraction distillation range 92-150 ℃, the third fraction distillation range 150-250 ℃, and the fourth fraction primary distillation point is more than 250 ℃. Wherein the distillate oil with the temperature of 150-250 ℃ is recycled to the inlet of the cracking reactor, and the distillate with the temperature of 150-250 ℃ accounts for about 35 weight percent of fresh feed to obtain>The BMCI value of the 250℃fraction was 13.2 and the paraffin content was 72%.
Example 8
Straight-run diesel oil B+10% coked diesel oil is used as a raw material, and the raw material properties are shown in table 1. Through the hydrofining and hydrocracking unit process, the pressure is 6.5Mpa, the hydrogen-oil ratio is 800, and the refining and cracking airspeed are respectively 2.0h based on fresh material -1 The refining temperature is 350 ℃, the cracking temperature is 350 ℃, the first fraction distillation range IBP-92 ℃, the second fraction distillation range 92-150 ℃, the third fraction distillation range 150-250 ℃, and the fourth fraction primary distillation point is more than 250 ℃. Wherein the distillate oil at 150-250deg.C is recycled, and the fraction at 150-250deg.C is about 19wt% of fresh feed>The BMCI value of the 250℃fraction was 13 and the paraffin content 71%.
TABLE 1 basic Properties of straight run Diesel
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A process for producing an ethylene feedstock by diesel hydrocracking, comprising the steps of:
(a) Mixing the diesel raw material with hydrogen, and carrying out hydrofining and hydrocracking;
(b) After gas-liquid separation, steam stripping and fractionation, the hydrogenation mixture flow produced in the step (a) is respectively provided with a first distillation section, a second distillation section, a third distillation section and a fourth distillation section; the distillation range of the first distillation section is not more than 100 ℃, the final distillation point of the second distillation section is not more than 180 ℃, the final distillation point of the third distillation section is not more than 250 ℃, and the distillation range is preferably 180-250 ℃;
(c) And (3) fully refining the generated third fraction to hydrofining or feeding the third fraction to a hydrocracking reaction unit for recycling processing.
2. The method for producing ethylene raw material by diesel hydrocracking according to claim 1, wherein the diesel raw material is straight-run diesel and/or coker diesel.
3. The method for producing ethylene raw material by diesel hydrocracking according to claim 1, wherein the hydrofining process conditions are as follows: the reaction pressure is 6-15Mpa, preferably 6-10Mpa, the reaction temperature is 330-380 ℃, preferably 330-370 ℃, and the hydrocracking process conditions are as follows: the reaction pressure is 6-15Mpa, preferably 6-10Mpa, the reaction temperature is 330-390 ℃, preferably 345-370 ℃, and the reaction space velocity of refining and cracking is 0.5-3.0h -1 The hydrogen oil volume ratio is 500-1500 v/v, preferably 500-1000v/v.
4. The process for producing ethylene feedstock by diesel hydrocracking according to claim 1, characterized in that in step (c) the mass ratio of hydrofinishing feed or hydrocracking feed to the third fraction of the recycle is from 1:1 to 10:1, preferably from 3:1 to 10:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1903993A (en) * | 2005-07-26 | 2007-01-31 | 中国石油化工股份有限公司 | Hydrogenation cracking method to produce more raw material for making ethylene |
| CN102453535A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocracking method for reforming material yield increase |
| CN103013559A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Hydrocracking method for selective increasing of aviation kerosene yield |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903993A (en) * | 2005-07-26 | 2007-01-31 | 中国石油化工股份有限公司 | Hydrogenation cracking method to produce more raw material for making ethylene |
| CN102453535A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocracking method for reforming material yield increase |
| CN103013559A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Hydrocracking method for selective increasing of aviation kerosene yield |
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