CN110835550B - Hydrocracking method for producing chemical raw materials - Google Patents
Hydrocracking method for producing chemical raw materials Download PDFInfo
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- CN110835550B CN110835550B CN201810928456.2A CN201810928456A CN110835550B CN 110835550 B CN110835550 B CN 110835550B CN 201810928456 A CN201810928456 A CN 201810928456A CN 110835550 B CN110835550 B CN 110835550B
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- 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
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Abstract
The invention relates to the field of hydrocracking, and discloses a hydrocracking method for producing chemical raw materials, which comprises the following steps: sequentially introducing a hydrocracking raw material into a hydrogenation pretreatment reaction zone and a hydrocracking reaction zone for hydrogenation reaction to obtain a hydrocracking effluent; then fractionating the hydrocracked effluent; the hydrocracking raw material contains VGO fraction and DAO fraction, the DAO fraction accounts for 10-30 wt% of the total amount of the hydrocracking raw material, and the hydrogen partial pressure in the hydrocracking reaction zone is 20-80% of the hydrogen partial pressure in the hydrogenation pretreatment reaction zone. The method provided by the invention can greatly increase the heavy naphtha yield of the hydrocracking device and can produce high-quality DCC feed.
Description
Technical Field
The invention relates to the field of hydrocracking, in particular to a hydrocracking method for producing chemical raw materials.
Background
Worldwide propylene demand is expected to continue to increase over the next 20 years, with a major driving force coming from market demand for products such as polypropylene, acrylonitrile and phenolic resins; chinese propylene demand has increased beyond world average. Propylene is second only to ethylene an important petrochemical feedstock. About 70% of the propylene worldwide is now produced by steam cracking starting from light hydrocarbons, whereas the traditional steam cracking olefin production route suffers from its competitiveness in the context of globalization due to its excessive cost. Therefore, the development of a method for producing low-carbon olefins from heavy raw materials through catalytic cracking, catalytic cracking and other ways is a reasonable technical path for solving the problem of insufficient chemical raw materials.
The deep catalytic cracking process (DCC) is a catalytic cracking process developed on the basis of an FCC process and aims to produce a large amount of low-carbon olefins. Compared with the latter, DCC has the characteristics of high yield of propylene and p-xylene, so that the economy is relatively good; according to literature reports that the property of the raw material has a great influence on the propylene yield of the DCC unit, the paraffin-based VGO raw material is considered as the best cracking raw material, and the propylene yield can reach more than 23 percent, mainly because the paraffin content is higher.
The hydrocracking technology is characterized in that heavy fractions such as Vacuum Gas Oil (VGO) and the like react with hydrogen in the presence of a catalyst, so that the dual purposes of improving the product quality and lightening the heavy oil product are achieved. Hydrocracking yields a wide cut product from the gas, naphtha, middle distillate and unconverted tail oil fraction. The hydrocracking tail oil has high paraffin and naphthene content and low aromatic hydrocarbon content, and is a high-quality ethylene raw material prepared by steam cracking.
The solvent deasphalting device is a key device for further processing inferior raw materials and improving economic benefits of oil refining enterprises at present, can be matched with wax oil hydrogenation or residual oil hydrogenation of refineries for use, reduces or does not produce high-sulfur coke, and simultaneously improves liquid yield of the whole refinery and increases economic benefits. However, how to further process the DAO raw material is an urgent problem to be solved in refineries.
The reformer is an important secondary processing unit in a refinery for producing high octane gasoline blending components or for producing aromatic base stocks. The reformed gasoline has the characteristics of high octane number, no olefin, no sulfur and nitrogen impurities and the like, and is a high-quality gasoline blending component. Benzene, toluene and xylene are basic raw materials in petrochemical industry, and the oil generated by the reforming device is rich in benzene, toluene and xylene, and high-value aromatic hydrocarbon products can be obtained through separation.
Straight run naphtha is the primary source of reformer feed. For a long time, the yield of crude oil light oil is low in China, the straight-run naphtha is one of the raw materials of an ethylene unit, and the shortage of reforming raw materials becomes one of the main factors limiting the development of the reforming unit. The hydrocracking process is an important means for heavy oil conversion, and the obtained heavy naphtha has the characteristics of high aromatic hydrocarbon content and low sulfur and nitrogen impurity content, can be directly used as a high-quality reforming device for feeding, and makes up for the defects of the straight-run naphtha.
According to the demands of the market on propylene and heavy naphtha and the requirements of enterprises on DAO processing, a hydrocracking technology capable of blending DAO and producing heavy naphtha and high-quality tail oil is urgently needed.
CN1854263A discloses a hydrocracking method for producing chemical raw materials to the maximum, the heated raw oil and hydrogen enter a first reaction zone to contact with a hydrofining catalyst and a hydrocracking catalyst in turn, the reaction material flow is subjected to oil-gas separation, the obtained hydrogen-rich gas is compressed and then recycled with recycle hydrogen, the liquid is fractionated to obtain light naphtha, heavy naphtha, diesel oil fraction and tail oil fraction, wherein the diesel oil fraction is mixed with recycle hydrogen after being pressurized and then contacts with a hydrocracking catalyst in a second reaction zone, and the reaction material flow in the previous step are mixed and enter a separation and fractionation system. The method can produce more than 98% of chemical raw materials including liquefied gas, light naphtha, heavy naphtha and tail oil. This prior art proposes the concept of recycling diesel to the second hydrocracking reaction zone and then converting all to light components.
CN101117596A discloses a hydrogenation method capable of flexibly producing diesel oil and chemical raw materials. Three reactors are set up, namely a hydrotreating 1 reactor, a hydrocracking reactor and a hydrotreating 2 reactor. Wherein, the tail oil is recycled for producing diesel oil in a high yield, and the diesel oil is recycled for producing naphtha in a high yield. Also, the process proposes a concept for recycling the diesel fraction.
CN101173189A discloses a two-stage hydrocracking method for producing chemical raw materials. Characterized in that heavy raw oil and hydrogen are mixed and then enter a first-stage hydrotreating zone, hydrogen-rich gas obtained by separating first-stage effluent directly enters a second-stage hydrocracking reaction zone, and naphtha and tail oil obtained by separation are used as chemical raw materials. The middle distillate oil alone or mixed with other inferior distillate oil enters a second-stage hydrogenation treatment zone for cracking. The method provides a concept of circularly cracking the middle distillate to produce naphtha in more.
In addition, the aromatic hydrocarbon is an important chemical raw material, the heavy naphtha is used as the feed of a reforming device for producing the aromatic hydrocarbon, the market prospect is better, the yield of the heavy naphtha is increased along with the increase of the conversion rate, but the selectivity of the heavy naphtha is reduced along with the increase of the conversion rate, and the light naphtha has higher yield. Tail oil is also an important chemical raw material, and for a hydrocracking device, how to increase the yield of naphtha by reducing the yield of diesel oil while ensuring the same yield of tail oil is one of the problems to be solved urgently.
The current processing technology for producing heavy naphtha and high-quality tail oil mainly comprises the following points: (1) producing heavy naphtha and tail oil by adopting a one-pass process; (2) the diesel or middle distillate is recycled to the second cracking reaction zone to increase the yield of heavy naphtha.
However, for enterprises needing to produce heavy naphtha and high-quality product tail oil at the same time, the scheme has the following defects:
(1) the yield of heavy naphtha under one-time passing process is not enough to meet the product requirements of enterprises;
(2) after the yield of the heavy naphtha meets the enterprise requirements, the yield of the light naphtha or the light hydrocarbon is higher;
(3) after the yield of the heavy naphtha meets the enterprise requirements, the yield of the diesel oil is higher, and the yield of the tail oil is lower;
(4) the diesel oil or the middle distillate oil is recycled to the second cracking reactor, which is equivalent to the addition of a first-stage hydrocracking device, an additional reactor and a hydrogen recycling system are needed, the complexity of the device is increased, and the investment is increased.
Disclosure of Invention
The inventor of the invention finishes the technical scheme of the invention based on the following invention ideas:
in general, a one-pass process is an effective means for producing heavy naphtha, diesel oil and tail oil, and by improving the conversion depth, the yield of the heavy naphtha is correspondingly increased; correspondingly, the tail oil quality at high conversion depth is also improved. Therefore, the conversion depth is improved under the one-pass process, and the tail oil is properly lightened (the yield and the quality of the tail oil are not reduced), so that the aims of producing heavy naphtha in a large amount and producing the tail oil are fulfilled. However, in practical situations, the above solutions have disadvantages, which mainly appear in the following aspects:
(1) after the conversion rate is improved, the yield of light hydrocarbon and light naphtha is correspondingly greatly increased, and for a fixed hydrocracking device, the light hydrocarbon in a fractionation system of the fixed hydrocracking device often has a bottleneck, so that the improvement range of the conversion depth is limited;
(2) after the conversion rate is improved, the chemical hydrogen consumption is greatly increased; at the same time, the selectivity of the heavy naphtha is reduced (more light naphtha fraction is produced) and the aromatic potential of the heavy naphtha is reduced.
In addition, in the above-mentioned scheme, while the yield of heavy naphtha is increased, in order to keep the yield of tail oil constant, part of middle distillate is inevitably cut into tail oil, which is not favorable for improving the quality of tail oil.
In order to overcome the defects of the prior hydrocracking process technology that the heavy naphtha is produced simultaneously to improve the tail oil quality (a one-time process and the conversion depth is simply improved), some methods are also provided at present, for example, a method for recycling part or all of middle distillate oil (kerosene and diesel oil) to a second cracking reaction zone. This can greatly increase the yield of heavy naphtha, but the process is more complex and increases the investment.
Therefore, the present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a novel hydrocracking process for producing chemical feedstocks to achieve a more economical and efficient combination of producing heavy naphtha and high-quality DCC feeds.
In order to achieve the above object, the present invention provides a hydrocracking process for producing a chemical raw material, comprising: sequentially introducing a hydrocracking raw material into a hydrogenation pretreatment reaction zone and a hydrocracking reaction zone for hydrogenation reaction to obtain a hydrocracking effluent; then fractionating the hydrocracked effluent; the hydrocracking raw material contains VGO fraction and DAO fraction, the DAO fraction accounts for 10-30 wt% of the total amount of the hydrocracking raw material, and the hydrogen partial pressure in the hydrocracking reaction zone is 20-80% of the hydrogen partial pressure in the hydrogenation pretreatment reaction zone.
The method provided by the invention can realize production of heavy naphtha and high-quality DCC feeding on the premise of reducing equipment investment.
The method provided by the invention can greatly increase the heavy naphtha yield of the hydrocracking device and can produce high-quality DCC feed. Compared with the method in the prior art, the method of the invention has the advantages that the selectivity of heavy naphtha is better, the aromatic hydrocarbon is higher, and the heavy naphtha is a better quality reformer feed; the tail oil has better quality and is fed by DCC with higher quality; in addition, the hydrogen consumption is low, and the device investment is also small.
Drawings
Many devices such as pumps, heat exchangers, compressors, etc. have been omitted from the drawings, but are well known to those skilled in the art.
FIG. 1 is a process flow diagram of a hydrocracking process for producing chemical feedstocks according to a preferred embodiment of the present invention.
Description of the reference numerals
1. Hydrocracking feedstock
2. Hydrogenation pretreatment reaction zone
3. Hydrocracking reaction zone
4. Separation and fractionation unit
5. Light naphtha fraction
6. Heavy naphtha fraction
7. Diesel oil fraction
8. Tail oil fraction
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the present invention provides a hydrocracking process for producing a chemical feedstock, the process comprising: sequentially introducing a hydrocracking raw material into a hydrogenation pretreatment reaction zone and a hydrocracking reaction zone for hydrogenation reaction to obtain a hydrocracking effluent; then fractionating the hydrocracked effluent; the hydrocracking raw material contains VGO fraction and DAO fraction, the DAO fraction accounts for 10-30 wt% of the total amount of the hydrocracking raw material, and the hydrogen partial pressure in the hydrocracking reaction zone is 20-80% of the hydrogen partial pressure in the hydrogenation pretreatment reaction zone.
By adopting the method provided by the invention, the overall selectivity of naphtha fraction can be effectively improved, the yield of diesel oil fraction is reduced, and the yield of tail oil fraction is maintained; and the selectivity of heavy naphtha is emphatically improved, and the aromatic potential of naphtha is favorably improved.
In order to further improve the quality of the tail oil, more preferably, the hydrogen partial pressure in the hydrocracking reaction zone is 30-70% of the hydrogen partial pressure in the hydrogenation pretreatment reaction zone.
According to a preferred embodiment, the hydrogen partial pressure in the hydrogenation pretreatment reaction zone is 14 to 20 MPa.
Preferably, the DAO fraction accounts for 10 to 30 wt% of the total amount of the hydrocracking feedstock.
Preferably, the conditions of the hydrogenation reaction in the hydrogenation pretreatment reaction zone are controlled so that the content of aromatic hydrocarbons in the hydrogenation pretreatment-produced oil obtained from the hydrogenation pretreatment reaction zone is not higher than 15% by weight.
Preferably, the conditions of the hydrogenation reaction in the hydrogenation pretreatment reaction zone are controlled so that the content of aromatic hydrocarbons in the hydrogenation pretreatment product oil obtained from the hydrogenation pretreatment reaction zone is not higher than 10% by weight.
In the present invention, there is no particular limitation on the specific kinds of the hydrotreating pretreatment catalyst and the hydrocracking catalyst, and they may be catalysts conventionally used in the art for hydrotreating and hydrocracking, respectively, and one hydrotreating pretreatment catalyst and one hydrocracking catalyst are exemplarily selected in the examples of the present invention, and those skilled in the art should not be construed as limiting the present invention.
In order to further improve the quality of the tail oil, preferably, the hydrogenation pretreatment reaction zone is filled with a hydrogenation pretreatment catalyst, and the hydrogenation pretreatment catalyst contains a carrier and an active metal element loaded on the carrier, and optionally contains an auxiliary agent element, wherein the carrier is selected from at least one of silicon oxide, aluminum oxide and silicon oxide-aluminum oxide, the active metal element is selected from at least one of a VIB group metal element and a VIII group metal element, and the auxiliary agent element is selected from at least one of boron, fluorine and phosphorus.
More preferably, the hydrogenation pretreatment catalyst contains 1 to 10 wt% of nickel element calculated by oxide, 10 to 50 wt% of molybdenum element and/or tungsten element calculated by oxide, 0.5 to 8 wt% of phosphorus element calculated by oxide, 1 to 10 wt% of fluorine element calculated by element, and the balance of silica-alumina carrier based on the total amount of the hydrogenation pretreatment catalyst.
More preferably, in the hydrotreating catalyst, the silica-alumina has a silica content of 2 to 45 wt% and the alumina content of 55 to 98 wt%, based on the total weight of the silica-alumina.
In order to further improve the quality of the tail oil, preferably, the hydrocracking reaction zone is filled with a hydrocracking catalyst, and the hydrocracking catalyst comprises a carrier and an active component loaded on the carrier, and the active component is selected from at least one of nickel, molybdenum, tungsten and cobalt.
More preferably, the hydrocracking catalyst contains nickel in an amount of 1 to 10 wt% as an oxide, tungsten in an amount of 10 to 50 wt% as an oxide, and optionally molybdenum in an amount of 1 to 15 wt% as an oxide, based on the total weight of the hydrocracking catalyst.
More preferably, in the hydrocracking catalyst, the carrier contains alumina and a zeolite molecular sieve.
More preferably, in the hydrocracking catalyst, the content of the alumina in the carrier is 30 to 80 wt% and the content of the zeolite molecular sieve is 2 to 70 wt% based on the carrier.
According to a preferred embodiment, the hydrogenation reaction conditions of the hydrogen pretreatment reaction zone include: the airspeed is 0.6-1.5 h-1The volume ratio of hydrogen to oil at the inlet is 700-1000, and the reaction temperature is 340-425 ℃.
According to a preferred embodiment, the hydrogenation reaction conditions of the hydrocracking reaction zone include: the airspeed is 1.0-2.5 h-1The reaction temperature is 360-425 ℃.
Preferably, the hydrocracked effluent is fractionated to obtain a light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction.
A preferred embodiment of the hydrocracking process for producing chemical feedstocks according to the present invention is provided below with reference to fig. 1, and comprises:
adding the hydrocracking raw material 1 and hydrogen into a hydrogenation pretreatment reaction zone 2 for hydrogenation pretreatment, and after the hydrogenation pretreatment, adding the hydrocracking raw material and the hydrogen into a hydrocracking reaction zone 3 for hydrocracking reaction to obtain a hydrocracking effluent; the hydrocracked effluent is then introduced into a separation and fractionation unit 4 for fractionation to obtain a light naphtha fraction 5, a heavy naphtha fraction 6, a diesel fraction 7 and a tail oil fraction 8; wherein the hydrocracking raw material 1 contains VGO fraction and DAO fraction, the DAO fraction accounts for 10-30 wt% of the total amount of the hydrocracking raw material 1, and the hydrogen partial pressure in the hydrocracking reaction zone 3 is 20-80% of the hydrogen partial pressure in the hydrocracking pretreatment reaction zone 2.
The hydrocracking method for producing the chemical raw materials provided by the invention also has the following specific advantages:
(1) the reaction activity of the hydrocracking catalyst is improved;
(2) the BMCI value of the tail oil is basically not reduced;
(3) on the premise of the same naphtha yield, the aromatic hydrocarbon of naphtha can be improved;
(4) the yield of the middle distillate oil is reduced, and the selectivity of naphtha is improved;
(5) the selectivity of the heavy naphtha can be improved, and the potential aromatic content of the heavy naphtha can be improved;
(6) and the hydrogen consumption can be saved, and the investment cost of the device can be reduced.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
The properties of the reaction raw materials in examples and comparative examples are shown in table 1.
TABLE 1
| | Starting materials | 1 | Raw material 2 |
| Description of the raw materials/weight percent | 70％VGO+30％DAO | 90％VGO+10％DAO | |
| Density (20 ℃ C.)/(g/cm)3) | 0.9238 | 0.9202 | |
| Sulfur mass fraction/% | 2.04 | 2.43 | |
| Mass fraction of nitrogen/(μ g/g) | 1112 | 859 | |
| Distillation range (D-1160)/. deg.C | |||
| Initial boiling point | 291 | 283 | |
| 10％ | 405 | 396 | |
| 30％ | 453 | 444 | |
| 50％ | 479 | 464 | |
| 70％ | 509 | 481 | |
| 90％ | 597 | 521 | |
| End point of distillation | 661 | 645 |
Example 1
A light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction were obtained in the production scheme of example 1 (carried out using the process flow shown in fig. 1) using a hydrotreating pretreatment catalyst RN-410 and a hydrocracking catalyst RHC-210, with the hydrotreating pretreatment catalyst RN-410 being filled in a hydrotreating pretreatment reaction zone and the hydrocracking catalyst RHC-210 being filled in a hydrocracking reaction zone, and using the raw material 1 in table 1 as a feedstock.
The process conditions, product distribution and key product properties are listed in tables 2 and 3.
As shown in tables 2 and 3, when the raw material 1 was subjected to the cracking reaction by the method in example 1 under the conditions of a medium pressure of 11MPa of the hydrocracking hydrogen partial pressure and a hydrocracking reaction temperature of 375 ℃, the total yield of naphtha + tail oil was 70.2%, the selectivity of naphtha was 50.1%, the selectivity of heavy naphtha fraction was 82.9%, the yield was 24.8%, and the aromatics were 56.8%, and the raw material was fed to a high-quality reformer, and further, the yield of tail oil fraction was 40.3%, the BMCI value was 13.0, and the hydrogen mass fraction was 14.1%, and the raw material was fed to a high-quality DCC device.
Compared with the comparative example 1, the hydrocracking hydrogen partial pressure of the example 1 is lower by about 3.5MPa, under the condition of similar yield of the tail oil, the yield of the chemical raw materials (naphtha + tail oil) in the example 1 of the invention is about 1.1 percent, the yield of the heavy naphtha is about 1.5 percent, the aromatic hydrocarbon is 2.4 percent, and the BMCI value and the hydrogen mass fraction of the tail oil are basically equivalent.
The method can give consideration to both heavy naphtha and tail oil, and the tail oil has excellent quality while producing more heavy naphtha.
TABLE 2
1) Naphtha selectivity: mass fraction of naphtha fraction yield to (naphtha + diesel) yield
2) Heavy naphtha selectivity: mass fraction of heavy naphtha yield to total naphtha yield
TABLE 3
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Heavy naphtha | ||||||
| Density at 20 deg.C/(g/mL) | 0.7487 | 0.7510 | 0.7548 | 0.7527 | 0.7464 | 0.7451 |
| Length of ar | 56.8 | 59.4 | 61.9 | 60.3 | 54.4 | 53.2 |
| Distillation Range (D-86)/. deg.C | ||||||
| IBP | 78 | 75 | 73 | 77 | 76 | 77 |
| 10％ | 104 | 106 | 102 | 100 | 104 | 105 |
| 50％ | 128 | 129 | 124 | 123 | 126 | 127 |
| 90％ | 162 | 160 | 153 | 156 | 160 | 157 |
| FBP | 179 | 178 | 174 | 177 | 174 | 175 |
| Tail oil | ||||||
| Density at 20 deg.C/(g/mL) | 0.842 | 0.8422 | 0.8423 | 0.8389 | 0.8418 | 0.8387 |
| Distillation range (D-1160)/. deg.C | ||||||
| IBP | 289 | 289 | 288 | 286 | 289 | 287 |
| 10％ | 345 | 346 | 346 | 342 | 345 | 343 |
| 50％ | 448 | 449 | 449 | 437 | 448 | 436 |
| 90％ | 506 | 507 | 507 | 493 | 506 | 494 |
| 95％ | 537 | 539 | 542 | 519 | 535 | 518 |
| Mass fraction of hydrogen/% | 13.0 | 13.0 | 13.1 | 12.4 | 12.9 | 12.3 |
Example 2
A light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction were obtained in the production scheme of example 2 (carried out using the process flow shown in fig. 1) using a hydrotreating pretreatment catalyst RN-410 and a hydrocracking catalyst RHC-210, with the hydrotreating pretreatment catalyst RN-410 being filled in a hydrotreating pretreatment reaction zone and the hydrocracking catalyst RHC-210 being filled in a hydrocracking reaction zone, and using the raw material 1 in table 1 as a feedstock.
The process conditions, product distribution and key product properties are listed in tables 2 and 3.
As shown in tables 2 and 3, when the raw material 1 was subjected to the cracking reaction by the method in example 2 under the conditions of a hydrocracking hydrogen partial pressure of 8MPa and a hydrocracking reaction temperature of 373 ℃, the total yield of naphtha + tail oil reached 72.0%, the selectivity for naphtha was 52.9%, the selectivity for heavy naphtha fraction reached 83.5%, the yield was 26.3%, and the aromatic hydrocarbon reached 59.4%, and the raw material was fed to a high-quality reformer, and the yield for tail oil fraction was 40.5%, the BMCI value was 13.0, and the hydrogen mass fraction was 14.09%, and the raw material was able to be fed to a high-quality DCC device.
Compared with the comparative example 1, the hydrocracking hydrogen partial pressure of the embodiment is lower by about 6.5MPa, the yield of chemical raw materials (naphtha + tail oil) is higher by about 2.9 percent, the yield of heavy naphtha is higher by about 3.0 percent, the heavy arene potential is higher by 5.0 percent, and the BMCI value and the hydrogen mass fraction of the tail oil are basically equivalent. The method can give consideration to both heavy naphtha and tail oil, and the heavy naphtha and chemical raw materials are produced more, and the quality of the heavy naphtha and the tail oil is also excellent.
Example 3
A light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction were obtained in the production scheme of example 3 (carried out using the process flow shown in fig. 1) using a hydrotreating pretreatment catalyst RN-410 and a hydrocracking catalyst RHC-210, with the hydrotreating pretreatment catalyst RN-410 being filled in a hydrotreating pretreatment reaction zone and the hydrocracking catalyst RHC-210 being filled in a hydrocracking reaction zone, and using the raw material 1 in table 1 as a feedstock.
The process conditions, product distribution and key product properties are listed in tables 2 and 3.
As shown in tables 2 and 3, when the raw material 1 was subjected to the cracking reaction by the method in example 3 under the conditions of a low pressure of 4MPa of the hydrocracking hydrogen partial pressure and a hydrocracking reaction temperature of 375 ℃, the total yield of naphtha + tail oil reached 73.5%, the selectivity of naphtha was 55.7%, the selectivity of heavy naphtha fraction was 84.7%, the yield was 28.2%, and the aromatics were 61.9%, and the raw material was fed to a high-quality reformer, and the yield of tail oil fraction was 40.2%, the BMCI value was 13.1, and the hydrogen mass fraction was 14.08%, and the raw material was able to be fed to a high-quality DCC.
Compared with the comparative example 1, the hydrocracking hydrogen partial pressure of the embodiment is lower by about 10.5MPa, the yield of chemical raw materials (naphtha + tail oil) is higher by about 4.4 percent, the yield of heavy naphtha is higher by about 4.9 percent, the heavy arene potential is higher by 7.5 percent, and the BMCI value and the hydrogen mass fraction of the tail oil are basically consistent. The method can give consideration to both heavy naphtha and tail oil, and the heavy naphtha and chemical raw materials are produced more, and the quality of the heavy naphtha and the tail oil is also excellent.
Example 4
A light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction were obtained in the production scheme of example 4 (carried out using the process flow shown in fig. 1) using a hydrotreating pretreatment catalyst RN-410 and a hydrocracking catalyst RHC-210, with the hydrotreating pretreatment catalyst RN-410 being filled in a hydrotreating pretreatment reaction zone and the hydrocracking catalyst RHC-210 being filled in a hydrocracking reaction zone, and using the raw material 2 in table 1 as a feedstock.
The process conditions, product distribution and key product properties are listed in tables 2 and 3.
As shown in tables 2 and 3, when the raw material 2 was subjected to the cracking reaction by the method in example 4 under the conditions of a hydrocracking hydrogen partial pressure of 8MPa and a hydrocracking reaction temperature of 374 ℃, the total yield of naphtha + tail oil reached 72.8%, the selectivity of naphtha was 54.4%, the selectivity of heavy naphtha fraction reached 84.3%, the yield was 27.3%, and the aromatic hydrocarbon reached 60.3%, and the raw material was fed to a high-quality reformer, and the yield of tail oil fraction was 40.4%, the BMCI value was 12.4, and the hydrogen mass fraction was 14.21%, and the raw material was able to be fed to a high-quality DCC device.
Compared with the comparative example 2, the hydrocracking hydrogen partial pressure of the embodiment is lower by about 6.5MPa, the hydrocracking reaction temperature is lower by about 2 ℃, and the yield of the tail oil is basically equivalent, but the yield of the chemical raw materials (naphtha + tail oil) is higher by about 4.2%, the yield of the heavy naphtha is higher by about 4.5 percentage points, the heavy aromatics potential is higher by 7.1%, and the BMCI value of the tail oil is basically equivalent. The method can give consideration to both heavy naphtha and tail oil, and the heavy naphtha and chemical raw materials are produced more, and the quality of the heavy naphtha and the tail oil is also excellent.
Comparative example 1
A light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction were obtained in the production scheme of comparative example 1 (carried out using the process flow shown in fig. 1) using a hydrotreating pretreatment catalyst RN-410 and a hydrocracking catalyst RHC-210, with the hydrotreating pretreatment catalyst RN-410 being filled in a hydrotreating pretreatment reaction zone and the hydrocracking catalyst RHC-210 being filled in a hydrocracking reaction zone, and with feed 1 in table 1 as feed.
The process conditions, product distribution and key product properties are listed in tables 2 and 3.
As shown in tables 2 and 3, after the raw material 1 was subjected to the cracking reaction by the method of comparative example 1 under the conditions of a hydrocracking hydrogen partial pressure of 14.5MPa and a hydrocracking reaction temperature of 375 ℃, the total yield of naphtha + tail oil was 69.1%, the selectivity of naphtha was 48.1%, the selectivity of heavy naphtha fraction was 81.5%, the yield was 23.3%, the aromatic hydrocarbon was 54.4%, and the yield of tail oil fraction was 40.5%, and the BMCI value was 12.9.
However, the hydrogen partial pressure was higher in this comparative example than in examples 1 to 3, but the chemical feedstock (naphtha + tail) yield was low, the naphtha selectivity was low, the heavy naphtha selectivity was slightly low, and the heavy naphtha aromatic potential was small.
Comparative example 2
A light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction were obtained in the production scheme of comparative example 2 (carried out using the process flow shown in fig. 1) using a hydrotreating pretreatment catalyst RN-410 and a hydrocracking catalyst RHC-210, with the hydrotreating pretreatment catalyst RN-410 being filled in a hydrotreating pretreatment reaction zone and the hydrocracking catalyst RHC-210 being filled in a hydrocracking reaction zone, and with feed 2 in table 1 as the feed.
The process conditions, product distribution and key product properties are listed in tables 2 and 3.
As shown in tables 2 and 3, when the raw material 2 was subjected to the cracking reaction by the method of comparative example 2 under the conditions of a hydrocracking hydrogen partial pressure of 14.5MPa and a hydrocracking reaction temperature of 376 ℃, the total yield of naphtha + tail oil was 68.6%, the selectivity of naphtha was 47.1%, the selectivity of heavy naphtha fraction was 81.4%, the yield was 22.8%, the aromatic hydrocarbon content was 53.2%, and the yield of tail oil fraction was 40.6%, the BMCI value was 12.3, and the hydrogen mass fraction was 14.22%.
Compared with example 4, under the condition of basically equivalent yield of tail oil, the hydrogen partial pressure required by comparative example 2 is higher, the required cracking temperature is higher, but the yield of chemical raw materials (naphtha + tail oil) is lower, the naphtha selectivity is lower, the heavy naphtha selectivity is slightly lower, and the heavy naphtha aromatic potential is smaller.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. A hydrocracking process for the production of a chemical feedstock, the process comprising: sequentially introducing a hydrocracking raw material into a hydrogenation pretreatment reaction zone and a hydrocracking reaction zone for hydrogenation reaction to obtain a hydrocracking effluent; then fractionating the hydrocracked effluent; the hydrocracking raw material contains VGO fraction and DAO fraction, the DAO fraction accounts for 10-30 wt% of the total amount of the hydrocracking raw material, and the hydrogen partial pressure in the hydrocracking reaction zone is 20-80% of the hydrogen partial pressure in the hydrogenation pretreatment reaction zone.
2. The process of claim 1, wherein the hydrogen partial pressure in the hydrocracking reaction zone is 30 to 70% of the hydrogen partial pressure in the hydrotreating pretreatment reaction zone.
3. The method according to claim 1 or 2, wherein the hydrogen partial pressure in the hydrotreating pretreatment reaction zone is 14 to 20 MPa.
4. The method according to claim 1 or 2, wherein the conditions of the hydrogenation reaction in the hydrogenation pretreatment reaction zone are controlled so that the aromatic hydrocarbon content in the hydrogenation pretreatment produced oil obtained from the hydrogenation pretreatment reaction zone is not higher than 15% by weight.
5. The method according to claim 4, wherein the conditions of the hydrogenation reaction in the hydrogenation pretreatment reaction zone are controlled so that the aromatic hydrocarbon content in the hydrogenation pretreatment produced oil obtained in the hydrogenation pretreatment reaction zone is not higher than 10% by weight.
6. The method according to claim 1 or 2, wherein the hydrogenation pretreatment reaction zone is filled with a hydrogenation pretreatment catalyst, and the hydrogenation pretreatment catalyst contains a carrier and an active metal element loaded on the carrier, and optionally contains an auxiliary element, wherein the carrier is selected from at least one of silicon oxide, aluminum oxide and silicon oxide-aluminum oxide, the active metal element is selected from at least one of a VIB group metal element and a VIII group metal element, and the auxiliary element is selected from at least one of boron, fluorine and phosphorus.
7. The method according to claim 6, wherein the hydrotreating catalyst contains 1 to 10 wt% of nickel element in terms of oxide, 10 to 50 wt% of molybdenum element and/or tungsten element in terms of oxide, 0.5 to 8 wt% of phosphorus element in terms of oxide, 1 to 10 wt% of fluorine element in terms of element, and the balance of silica-alumina carrier, based on the total amount of the hydrotreating catalyst.
8. The method according to claim 7, wherein the silica-alumina is contained in an amount of 2 to 45 wt% and the alumina is contained in an amount of 55 to 98 wt% based on the total weight of the silica-alumina in the hydrotreating catalyst.
9. The process according to claim 1 or 2, wherein the hydrocracking reaction zone is packed with a hydrocracking catalyst, and the hydrocracking catalyst comprises a carrier and an active component selected from at least one of nickel, molybdenum, tungsten and cobalt supported on the carrier.
10. The process according to claim 9, wherein the hydrocracking catalyst contains nickel in an amount of 1 to 10 wt% as an oxide, tungsten in an amount of 10 to 50 wt% as an oxide, and optionally molybdenum in an amount of 1 to 15 wt% as an oxide, based on the total weight of the hydrocracking catalyst.
11. The process of claim 9 wherein in the hydrocracking catalyst, the support comprises alumina and a zeolitic molecular sieve.
12. The method of claim 11, wherein the hydrocracking catalyst contains 30 to 80 wt% of the alumina and 2 to 70 wt% of the zeolite molecular sieve based on the carrier.
13. The method of claim 1 or 2, wherein the hydrogenation reaction conditions of the hydrogenation pretreatment reaction zone comprise: the airspeed is 0.6-1.5 h-1The volume ratio of hydrogen to oil at the inlet is 700-1000, and the reaction temperature is 340-425 ℃.
14. The process of claim 1 or 2, wherein the hydrogenation reaction conditions of the hydrocracking reaction zone comprise: the airspeed is 1.0-2.5 h-1The reaction temperature is 360-425 ℃.
15. The process according to claim 1 or 2, wherein the hydrocracked effluent is fractionated to obtain a light naphtha fraction, a heavy naphtha fraction, a diesel fraction and a tail oil fraction.
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| CN101117596A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Hydrogenation method capable of producing diesel oil and chemical materials flexibly |
| CN101173189A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Two-stage hydrogenation cracking method for producing industrial chemicals |
| CN107987879A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of and method for hydrogen cracking of production heavy naphtha and tail oil |
| CN108003927A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking for producing boat coal |
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| CN101117596A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Hydrogenation method capable of producing diesel oil and chemical materials flexibly |
| CN101173189A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Two-stage hydrogenation cracking method for producing industrial chemicals |
| CN107987879A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of and method for hydrogen cracking of production heavy naphtha and tail oil |
| CN108003927A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking for producing boat coal |
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