CN108165294B - Oil-coal co-refining method using short-cycle hydrogen supply solvent oil - Google Patents
Oil-coal co-refining method using short-cycle hydrogen supply solvent oil Download PDFInfo
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- CN108165294B CN108165294B CN201611151607.5A CN201611151607A CN108165294B CN 108165294 B CN108165294 B CN 108165294B CN 201611151607 A CN201611151607 A CN 201611151607A CN 108165294 B CN108165294 B CN 108165294B
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Images
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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
Abstract
A method for oil-coal co-refining with short-cycle hydrogen-supplying solvent oil, the hydrocarbon oil in the hot high-molecular gas R10P-HS-V of the product R10P obtained in the hydrogenation reaction process R10 of oil-coal co-refining after blending coal slurry with non-coal derived oil is converted into a product R30P containing R30P and separated into gas phase R30P-V and oil phase R30P-L through the on-line hydrogenation modification reaction process R30, at least a part of the oil phase R30P-L containing material flow enters R10 to be used as short-process cycle hydrogen-supplying agent SR-LBDS, and the 'rich active hydrogen' reaction condition is manufactured at low cost; the product obtained by pressurizing the R10P-HS-V high temperature and high temperature oil R10P-MS-L and then entering the preposed R30 enters R10 in a self-pressure mode, so that the process is more concise; r10 can be used in high-concentration coal-oil slurry, pre-hydrogenation section, interstage gas-liquid separation process, batch classification injection hydrogen supply solvent, and hydrogen gas stripping type thermal high-concentration product.
Description
Technical Field
The invention relates to a method for oil-coal co-refining by using short-cycle hydrogen-supplying solvent oil, wherein hydrocarbon oil in hot high-molecular gas R10P-HS-V of a product R10P obtained in an oil-coal co-refining hydrogenation reaction process R10 is pressed after non-coal derived oil is mixed with coal slurry, the hydrocarbon oil is converted into a product R30P containing R30P and separated into a product R30P containing gas phase R30P-V and oil phase R30P-L through an online solvent oil hydrogenation modification reaction process R30, at least one part of oil phase R30P-L-containing material flow enters R10 to be used as a short-process cycle hydrogen-supplying agent SR-LBDS, and the reaction condition of 'rich in active hydrogen' is manufactured at low cost; the method comprises the following steps of pressurizing R10P-HS-V high temperature and high temperature oil R10P-HS-V-MS-L, feeding the pressurized oil into a front-arranged R30, and feeding the obtained product into R10 in a self-pressure mode, so that the process is more concise; r10 can be used in high-concentration coal-oil slurry, pre-hydrogenation section, interstage gas-liquid separation process, batch classification injection hydrogen supply solvent, and hydrogen gas stripping type thermal high-concentration product.
Background
Oil-coal co-refining refers to co-processing of coal and non-coal derived oil simultaneously.
The hydrogen donor hydrocarbon refers to a hydrocarbon component with a hydrogen donor function in the direct coal hydrogenation oil-making reaction process, and the hydrogen donor hydrocarbon comprises partially saturated bicyclic aromatic hydrocarbons and partially saturated polycyclic aromatic hydrocarbons, and is an ideal component of hydrogen donor solvent oil used in the direct coal hydrogenation liquefaction process. In the hydrogen supply hydrocarbon, the hydrogen supply speed of a dihydro body is higher than that of a tetrahydro body, and the hydrogen supply speed of the dihydro body of tricyclic aromatic hydrocarbon is higher or lower than that of the dihydro body of bicyclic aromatic hydrocarbon; tests have demonstrated that polycyclic aromatic hydrocarbons, although not having a hydrogen donating ability, have the ability to transfer hydrogen. The relative hydrogen supply rates at 400 ℃ for the following components were as follows:
the hydrogen donor solvent oil refers to hydrocarbon oil rich in hydrogen donor hydrocarbon.
As for the existing oil-coal refining method, a document for recording such data is disclosed in A01: ① publication name, modern coal chemical engineering technical handbook, pages 1060 to 1063, ② retrieval uses a book code, namely an ISBN code, 978-7-122-09636-4, a Chinese edition library CIP data check character (2010) No. 197010, ③ editions, Heyongde Master, ④ publication, chemical industry Press.
The raw oil AF used in the oil-coal co-refining process is typically a low value high boiling point material such as bitumen from the petroleum processing industry, extra heavy crude oil or petroleum residuum or tar liquid hydrocarbons.
In the oil-coal co-refining process, raw oil AF is used for preparing coal slurry and is used as a conveying medium of coal, but a hydrogen supply solvent oil loop is not arranged, and the basic process can be a single-stage process or a two-stage process. In the oil-coal co-refining process, most of the liquid product is derived from oil rather than from coal, and of course a small portion of the liquid product is produced from coal. The general aim of the oil-coal co-refining process is to improve the quality of petroleum derivatives while liquefying coal, and reduce the investment and operation cost of unit products. However, non-coal derived solvents have poor coal solubility and low hydrogen donating capacity, and therefore, the conversion rate to liquid products is relatively low.
In fact, the research history of the oil-coal co-refining process exceeds 45 years, but no commercial device construction and production exists until now.
In the existing oil-coal co-refining hydrogenation reaction method, in order to realize the aims of low investment and low operation cost, the precondition of no use of a circulating hydrogen supply solvent is adopted; in the oil-coal co-refining hydrogenation reaction process, a large amount of active hydrogen is needed for stabilizing free radicals generated by coal liquefaction, a large amount of active hydrogen is needed for stabilizing free radicals generated by raw oil thermal cracking, a large amount of active hydrogen is needed for the hydrogenation dissociation reaction for removing impurity elements such as oxygen, sulfur and nitrogen, a large amount of active hydrogen is needed, an unbalanced essential contradiction is formed between the inherent characteristics that a large amount of activity cannot be provided in the oil-coal co-refining hydrogenation reaction process, and a large amount of thermal condensation products such as coke are generated by the high-temperature thermal condensation reaction of macromolecular hydrocarbons under the reaction condition lacking active hydrogen, so that the oil-coal co-refining hydrogenation reaction process has extremely low conversion rate, and the large amount of coking reaction process cannot be continuously operated for a long time when the conversion rate is increased.
From the above analysis, the existing hydrogenation reaction method for oil-coal co-refining has the fundamental defects that a large amount of active hydrogen required by the reaction cannot be provided, and the existing hydrogenation reaction method for oil-coal co-refining can be remarkably improved by using the hydrogen-supplying solvent oil capable of effectively releasing the active hydrogen, but if a large-cycle hydrogen-supplying solvent oil loop similar to that used in the existing direct oil-making process for coal hydrogenation is adopted, and the hydrogen-supplying solvent oil is used for preparing coal slurry and serving as a conveying medium of coal, the investment and the operation cost of unit products in the whole process of oil-coal co-refining are greatly increased, and the economic competitiveness is lost.
In fact, the oil-coal co-refining process, the raw oil AF is used for preparing coal slurry and used as a conveying medium of coal, so the hydrogen-supplying solvent oil is not required to bear the tasks of preparing coal slurry and using as a conveying medium of coal, and only the function of "conveying sufficient amount of active hydrogen" is required, based on the analysis, the invention is expected to provide a low-cost method for conveying the hydrogen-supplying solvent oil to the oil-coal co-refining hydrogenation reaction process to manufacture the reaction condition of "rich active hydrogen", and the aim of the invention is how to construct the simplest circulation flow because the circulation solvent oil hydrogenation stabilization reaction process for preparing the circulation hydrogen-supplying solvent and the circulation conveying step of the hydrocarbon stream containing hydrogen are necessary steps. The hydrogen-supplying solvent oil conveying method for reference mainly comes from the hydrogen-supplying solvent oil conveying method in the direct coal hydrogenation liquefaction process. The direct coal hydrogenation liquefaction process refers to a coal hydrogenation liquefaction process for hydrogen-supplying solvent oil prepared from coal and coal derived oil at the same time.
The hydrogen-supplying solvent oil used in the direct coal hydrogenation liquefaction process and the method for conveying the same are described below.
In the direct coal hydrogenation liquefaction reaction process, a hydrogen supply solvent is essentially the most main foreground catalyst for the positive and negative reactions of coal liquefaction, rapidly provides most of active hydrogen in the coal liquefaction process, and directly determines the rapid hydrogenation stable speed of pyrolysis free radical fragments, so that the thermal condensation reaction is inhibited; in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite, molybdenum sulfide and the like are essentially retarders of coal liquefaction negative reactions, and solid catalyst particles adsorb colloid and asphaltene molecules MK with high viscosity and enable the MK to be in contact with active hydrogen on the surface of the solid catalyst, so that the thermal shrinkage of the MK is inhibited; in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite, molybdenum sulfide and the like are essentially simultaneously used as a recovery catalyst of a hydrogen donor dehydrogenation product SH-Z, solid catalyst particles adsorb SH-Z and enable SH-Z to be in contact with active hydrogen on the surface of the solid catalyst, so that hydrogenation is recovered into hydrogen-supplying hydrocarbon with hydrogen supply capacity, and the recovery speed of the hydrogen donor dehydrogenation product SH-Z is directly determined; in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite and the like are basically and simultaneously weak catalysts for target hydrocracking reactions such as the hydrocracking of asphaltene and preasphaltene. Therefore, in the direct coal hydrogenation liquefaction reaction process, solid catalysts such as pyrite and molybdenum sulfide are more like a catalyst operating in a background in a certain sense, and play a supporting and promoting role in coal liquefaction target product distillate oil. In the KR10 reaction process for producing oil by coal hydrogenation, the operation conditions and effects of the solvent oil hydrogenation stabilization reaction process are naturally extremely important, because the function of the hydrogen donor solvent DS is very important.
A document for recording such data about the existing coal hydrogenation direct liquefaction process and hydrogen supply solvent recycling method is disclosed in publication A01: ①, publication name of "coal direct liquefaction Process and engineering", pages 130 to 365, ②, retrieval of the code of the publication, ISBN code, 9-78703-04308-23, publication ③, Wu Xiu, Shu-Gong-Ping, Likejia, Xishun-Ming, publication No. ④, scientific Press.
The flow relationship between the online solvent oil hydrogenation modification reaction process of the existing coal hydrogenation direct liquefaction process and the KR10 flow process of the coal hydrogenation oil preparation reaction process is divided into an offline type solvent oil hydrogenation stabilization method, namely an independent high-pressure system, and a postposition online type solvent oil hydrogenation stabilization method, namely a high-pressure system which secondarily utilizes hot high-pressure gas of KR10 product KR10P to carry out solvent oil hydrogenation stabilization, so that the investment and the energy consumption are reduced; the off-line hydrogenation stabilization method has good product quality but large investment and can not be adopted by the method; while the post-on-line hydrogenation stabilization method saves investment, but the H in the KR10 product exists2O、NH3、H2S、CO、CO2HCl is introduced into the hydrogenation stabilization reaction process to deteriorate the hydrogenation stabilization reaction of the hydrogen donor solventThe significant drawbacks of the process catalyst operating performance (resulting in short catalyst life and unstable hydrogen donor solvent quality) are not exploited by the present invention.
The existing circulation methods of the hydrogen donor solvent obtained by the solvent oil hydrogenation stable reaction product of the direct coal hydrogenation liquefaction process are all to separate the hydrogenation stable reaction product to obtain a low-pressure hydrogen donor solvent, and then the low-pressure hydrogen donor solvent is used as a coal slurry preparation solvent under the low-pressure condition. In fact, with the long-term industrial successful operation of the preparation and conveying technology of the high-concentration coal-oil slurry, part of the hydrogen-supplying solvent can completely and directly enter the KR10 reaction process of directly preparing oil by coal hydrogenation under the conditions of high pressure and high temperature without the steps of depressurization, separation, coal slurry blending, coal slurry pressurized conveying, coal slurry high-pressure preheating and the like, so that short-flow circulation of part of the hydrogen-supplying solvent is formed, and the reaction condition of 'rich active hydrogen' is manufactured at low cost.
According to the concept, a short-cycle solvent oil hydrogenation modification reaction process R30 hydrogenation reaction process R30 using hydrocarbon oil in hot high-gas KR10P-HS-V as a precursor can be realized, and a long-cycle solvent oil hydrogenation modification reaction process R20 using distillate oil obtained by separating hot high-gas KR10P-HS-L as a precursor can exist, of course, high-pressure operation steps of R30 and R20 can be partially combined to simplify the process, and part of product solvent oil of R30 or R20 can be used as an ingredient of the oil coal slurry.
On the other hand, hydrogen supply solvents obtained from solvent naphtha hydrogenation stable reaction products of the existing coal hydrogenation direct liquefaction process enter the addition point of the KR10 in the coal hydrogenation direct liquefaction reaction process, and the hydrogen supply agents are injected from the reaction starting end and enter in a coal slurry batching mode, so that the hydrogen supply solvents cannot be uniformly dispersed in all reaction spaces.
The low boiling point recycle hydrogen donor LBDS and the high boiling point recycle hydrogen donor HBDS are analyzed below.
The low-boiling point circulating hydrogen donor LBDS refers to hydrogen donor hydrocarbons with the conventional boiling point of 250-400 ℃, and mainly comprises 2-ring, 3-ring and 4-ring structure hydrocarbons. The high-boiling-point circulating hydrogen donor HBDS refers to hydrogen donor hydrocarbons with a conventional boiling point of 400-530 ℃, and mainly refers to hydrocarbons with 4-ring and 5-ring structures.
Compared with a high boiling point hydrogen donor HBDS, LBDS is difficult to thermally crack due to small molecular weight, is high in movement speed due to small molecular weight, is short in residence time in a liquid phase space of KR10 due to low boiling point and easy to vaporize, and is capable of passing once in a gas phase, and has the advantages of low pyrolysis rate, high hydrogen supply speed and high hydrogen carrying load due to ideal molecular structure.
Compared with the low-boiling point circulating hydrogen donor LBDS, the high-boiling point hydrogen donor HBDS is easy to thermally crack due to the large molecular weight, namely the pyrolysis temperature is low, the movement speed of the large molecular weight is low, the boiling point is high and difficult to vaporize, the circulating residence time in the liquid phase space of KR10 is long, the hydrogen supply speed is low due to the complex molecular structure, and the heat condensation is easy, so that the high-boiling point hydrogen donor HBDS has the relative disadvantages of high pyrolysis rate, high condensate yield, low-speed hydrogen supply and low hydrogen carrying load; however, for the liquid-phase hydrocarbon component LC such as high-boiling-point free radicals, the high-boiling-point hydrogen donor HBDS is a reliable liquid-phase hydrogen donor for LC.
From the above analysis, in order to achieve KR10 coal conversion per pass, suppress the yield of thermal condensate, increase the hydrogenation depth of the product, and reduce the total temperature rise of KR10 reaction, it is necessary to achieve "a sufficient amount of hydrogen donor solvent is uniformly dispersed in all the reaction spaces" at low cost, and the principle of using hydrogen donor solvent oil should be:
① in order to increase the amount of hydrogen donor at low cost, a low-cost hydrogen donor circulation flow with a small number of steps, i.e., a short circulation flow, is required;
② in order to form "active hydrogen rich" liquid phase hydrogenation reaction conditions, the total hydrogen donor amount needs to be increased, and in order to reduce the thermal cracking rate of the recycle hydrogen donor, the amount of LBDS of the low boiling point recycle hydrogen donor should be increased as much as possible, for example, the amount of LBDS of the low boiling point recycle hydrogen donor is increased in the front or middle reaction zone of KR 10;
③ can use high concentration kerosene slurry technology, and a pre-hydrogenation section with lower reaction temperature for strengthening the hydrogen transfer liquid phase reaction ratio between hydrocarbon molecules, and consumes active hydrogen from the low boiling point hydrogen donor LBDS;
④, injecting low boiling point circulation hydrogen supply agent LBDS in sections, and realizing short-flow circulation by using an interstage gas-liquid separation process, injecting part of LBDS later and using a hydrogen gas stripping type heat high-separation mode for products;
⑤ part of high boiling point hydrogen donor HBDS is directly introduced into the rear reaction space of KR10 to directly increase the liquid phase hydrogen donor capacity;
⑥ can be provided with or combined with a high boiling point hydrogen donor HBDS hydrogenation process, and is especially suitable for large coal liquefaction devices.
The document A01, pages 214 to 216 of the coal direct liquefaction Process and engineering, describes the yields of impurities and gaseous hydrocarbons in KR10 in the hydrogenation stabilization reaction process of hydrogen donor solvent and the reaction process of coal hydrogenation for oil production, as shown in tables 1 and 2.
TABLE 1 BSU direct coal liquefaction material balance table
| Item | C.wt.%/maf% | C.wt.%/maf% | Out/maf.wt.% | Out/maf.wt.% | In-out/maf.wt.% |
| H2S | 0.00 | 0.00 | 0.72 | 0.68 | 0.72 |
| NH3 | 0.00 | 0.00 | 0.36 | 0.34 | 0.36 |
| CO | 0.00 | 0.00 | 0.99 | 0.94 | 0.99 |
| CO2 | 0.00 | 0.00 | 1.46 | 1.39 | 1.46 |
| C1 | 0.00 | 0.00 | 3.46 | 3.29 | 3.46 |
| C2 | 0.00 | 0.00 | 2.79 | 2.66 | 2.79 |
| C3 | 0.00 | 0.00 | 3.32 | 3.16 | 3.32 |
| C4 | 0.00 | 0.00 | 1.83 | 1.74 | 1.83 |
| Solvent(s) | 128.52 | 122.22 | 0.00 | 0.00 | -128.52 |
| Oil (< 220 ℃ C.) | 0.00 | 0.00 | 25.33 | 24.09 | 25.33 |
| Oil (> 220 ℃ C.) | 0.00 | 0.00 | 30.01 | 28.54 | 30.01 |
| Solvent raw material | 0.00 | 0.00 | 128.52 | 122.22 | 128.52 |
| H2O | 0.00 | 0.00 | 12.27 | 11.67 | 12.27 |
| Fraction above 538 deg.C | 0.00 | 0.00 | 15.21 | 14.46 | 15.21 |
| H2 | 5.65 | 5.37 | 0.00 | 0.00 | -5.65 |
| Anhydrous ashless base coal | 100.00 | 95.10 | 8.78 | 8.35 | -91.22 |
| Ash of | 5.15 | 4.90 | 5.15 | 4.90 | 0.00 |
| catalyst-Fe | 1.05 | 1.00 | 1.05 | 1.00 | 0.00 |
| Catalyst-other | 0.61 | 0.58 | 0.23 | 0.22 | -0.38 |
| Sulfur | 1.20 | 1.14 | 0.69 | 0.66 | -0.51 |
| DMDS | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Total up to | 242.18 | 230.32 | 242.18 | 230.32 | 0.00 |
TABLE 2 BSU solvent hydrogenation unit materials balance Table
| Item | C.wt.%/maf% | C.wt.%/maf% | Out/maf.wt.% | Out/maf.wt.% | In-out/maf.wt.% |
| H2S | 0.00 | 0.00 | 1.41 | 1.34 | 1.41 |
| NH3 | 0.00 | 0.00 | 0.21 | 0.20 | 0.21 |
| CO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CO2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| C1 | 0.00 | 0.00 | 0.71 | 0.68 | 0.71 |
| C2 | 0.00 | 0.00 | 0.03 | 0.02 | 0.03 |
| C3 | 0.00 | 0.00 | 0.03 | 0.02 | 0.03 |
| C4 | 0.00 | 0.00 | 0.03 | 0.03 | 0.03 |
| Solvent(s) | 0.00 | 0.00 | 128.73 | 122.42 | 128.73 |
| Oil (< 220 ℃ C.) | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Oil (> 220 ℃ C.) | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Solvent feed | 128.52 | 122.22 | 0.00 | 0.00 | -128.52 |
| H2O | 0.00 | 0.00 | 0.47 | 0.45 | 0.47 |
| Fraction above 538 deg.C | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| H2 | 1.16 | 1.11 | 0.00 | 0.00 | -1.16 |
| Anhydrous ashless base coal | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Ash of | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| catalyst-Fe | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Catalyst-other | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Sulfur | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| DMDS | 1.93 | 1.83 | 0.00 | 0.00 | -1.93 |
| Total up to | 131.61 | 125.16 | 131.61 | 125.16 | 0.00 |
For the hydrogen supply solvent hydrogenation stable reaction process RX0 and the coal hydrogenation oil production reaction process KR10, the following conclusions can be obtained by performing statistical comparison on the impurity content of the raw material, the impurity hydrogenation conversion rate and the gas hydrocarbon yield:
① liquefied coal is rich in impurities such as oxygen, sulfur and nitrogen, and its direct hydrogenation liquefaction process is a process with high conversion of impurities such as H2O、NH3、H2S、CO、CO2The yield of (2) is large;
② liquefied coal is high organic matter content coal, and its direct coal hydrogenation liquefaction process is high organic matter liquefaction conversion process, and conventional gas hydrocarbon such as CH4、C2、C3、C4The yield of (2) is large;
③ hydrogenation stabilizing reaction process for hydrogen-supplying solvent R20 raw material hydrocarbon, usually hydrocarbon with low content of hetero element such as oxygen, sulfur and nitrogen, and coal hydrogenation direct liquefaction process is usually process with low conversion rate of impurity such as H2O、NH3、H2S、CO、CO2The yield of (2) is small;
④ hydrogenation stabilization process for hydrogen-donating solvent RX0 is generally a process with relatively low cracking conversion, and is usually a process with conventional gaseous hydrocarbons such as CH4、C2、C3、C4The yield of (a) is small.
Based on the above conclusion, the invention considers that the quantity of impurity gas and gas hydrocarbon in the pre-solvent oil hydrogenation stable reaction process using new hydrogen and/or recycle hydrogen with extremely low impurity concentration is very small, so that the hot high-molecular gas RX0P-V obtained by separating RX0P product in the solvent oil hydrogenation stable reaction process RX0 can enter the coal hydrogenation oil-making reaction process KR10 to realize secondary effective utilization. Thus, the "H in R10 product" can be avoided2O、NH3、H2S、CO、CO2The HCl is introduced into a hydrogenation stabilization reaction process RX0 to deteriorate the operation efficiency of the catalyst, and meanwhile, the secondary use of the circulating hydrogen can be realized, a front-mounted solvent oil hydrogenation stabilization reaction process RX0 and a coal hydrogenation oil preparation reaction process KR10 combined method can be formed, and a coal direct oil preparation method or an oil-coal co-refining method using short-circulation hydrogen supply solvent oil with a simple flow is formed.
From the application effect of the known catalyst or process for the direct coal hydrogenation liquefaction process, large or industrial operation data such as coal liquefaction oil yield, reactor operability are inferior to the data and operation condition of a small-sized high-pressure stirred tank test device, and the inventor believes that the root cause of the difference is the following reasons, and the improvement of the catalyst or process can form an improved process:
① in the high-pressure stirring kettle, the hydrogen-supplying solvent with sufficient quantity is uniformly dispersed in all the reaction spaces, but the industrial device can not do the reaction at all, and only can carry out approximative operation;
at present, the known coal hydrogenation direct liquefaction process method almost injects a hydrogen donor from the initial space end of a reactor and enters the reactor in a coal slurry mixing mode;
② in the high-pressure stirring kettle, the gas phase reaction product can be separated from the liquid phase quickly and enter the gas phase at the upper part, almost no longer contacts with the liquid phase for reaction, but the industrial device can not do the same, and can not set enough middle gas-liquid separators to separate the gas phase product in time;
the existing coal hydrogenation direct liquefaction process method is difficult to simply realize intermediate gas-liquid separation operation, and a part of gas-phase products are separated out in time; almost all gas-liquid products are discharged from the tail end of the reactor in a cocurrent mode, and the repeated contact reaction of the gas-phase reaction products and the liquid phase is inevitable; intermediate product impurities such as H2O、NH3、H2S、CO、CO2The existence of HCl not only reduces the partial pressure of hydrogen, but also poisons the hydrogenation catalyst and occupies the volume of reaction space;
③ in the high-pressure stirring kettle reaction, the contact and separation frequency of the catalyst particles and the liquid phase material is very high, the contact efficiency of the catalyst surface and the liquid phase molecules is very high, but the industrial device can not do the same, only the approximative operation is carried out, such as increasing the liquid phase circulation volume, namely maintaining the ideal fluidization state of the catalyst in the liquid phase, namely strengthening the stirring effect, and reducing the catalyst particle size, namely increasing the catalyst dispersion degree.
So far, the basic idea of the invention has been formed: a method for oil-coal co-refining with short-cycle hydrogen-supplying solvent oil, the hydrocarbon oil in the hot high-molecular gas R10P-HS-V of the product R10P obtained in the hydrogenation reaction process R10 of oil-coal co-refining after blending coal slurry with non-coal derived oil is converted into a product R30P containing R30P and separated into gas phase R30P-V and oil phase R30P-L through the on-line hydrogenation modification reaction process R30, at least a part of the oil phase R30P-L containing material flow enters R10 to be used as short-process cycle hydrogen-supplying agent SR-LBDS, and the 'rich active hydrogen' reaction condition is manufactured at low cost; the method comprises the following steps of pressurizing R10P-HS-V high temperature and high temperature oil R10P-HS-V-MS-L, feeding the pressurized oil into a front-arranged R30, and feeding the obtained product into R10 in a self-pressure mode, so that the process is more concise; r10 can be used in high-concentration coal-oil slurry, pre-hydrogenation section, interstage gas-liquid separation process, batch classification injection hydrogen supply solvent, and hydrogen gas stripping type thermal high-concentration product.
The method of the present invention has not been reported.
In order to optimize the effect of the invention, the method can be combined with other various technologies to form a combined process.
At least a part of low boiling point hydrocarbon obtained by separating the hot high-fraction oil R10P-HS-L can be introduced into an online solvent hydrogenation stabilization reaction process RX0 to jointly produce short-process light hydrogen supply hydrocarbon and long-process light hydrogen supply hydrocarbon for coal blending slurry, and then, part of the hot high-fraction oil RX0P-HS-L enters a separation/fractionation process to separate the light hydrogen supply hydrocarbon for the coal blending slurry.
The solvent oil hydrogenation stabilizing reaction process R20 of the high boiling point hydrocarbon HBML obtained in the separation of the high boiling point hydrocarbon HBML R10P-HS-L and the short-flow solvent oil hydrogenation stabilizing reaction process R30 can be combined with a high pressure system, such as a part of the high boiling point hydrocarbon HBML solvent oil hydrogenation stabilizing reaction process R20 product R20P hot high pressure separator and a part of the high boiling point hydrocarbon HBML solvent oil in the short-flow online solvent hydrogenation reaction process R30 product R30P hot high pressure separator are mixed together and enter a separation/fractionation process to separate a coal blending slurry, namely, the coal blending slurry enters an initial hydrogenation liquefaction reaction process of R10, meanwhile, the residual part of the high boiling point hydrocarbon oil obtained in the short-flow online solvent hydrogenation reaction process R30 product R30P hot high pressure separator is introduced into an intermediate hydrogenation liquefaction reaction process of R10, and simultaneously the residual part of the high boiling point hydrocarbon HBML solvent oil hydrogenation stabilizing reaction process R20 product R20P hot high pressure separator is introduced into the residual part of R10 high boiling point hydrocarbon HBML solvent oil hydrogenation stabilizing reaction process R3552 product R P In the hydrogenation liquefaction reaction process, the hydrogen donor solvent is injected in batches in a classified manner, so that 'the hydrogen donor solvent with sufficient quantity is uniformly dispersed in all reaction spaces' is reasonably realized.
The post-positioned on-line solvent oil hydrogenation stable reaction process R30 can use hot high-molecular gas R10P-HS-V as feed, can use condensed oil in the temperature high-molecular process of the hot high-molecular gas R10P-HS-V as feed, can use hydrogen gas stripping of the condensed oil in the temperature high-molecular process of the hot high-molecular gas R10P-HS-V as feed, can process other similar materials simultaneously, and enters the direct coal hydrogenation liquefaction process R10 after the short-cycle light cycle hydrogen supply agent SR-LBDS is pressurized.
The preposed online solvent hydrogenation reaction process R30 can process the pressurized liquid of the condensed oil in the temperature and high-temperature separation process of the hot high-temperature separation gas R10P-HS-V, can process other similar materials simultaneously, and the short-circulation light-weight circulation hydrogen supply agent SR-LBDS can enter the direct coal hydrogenation liquefaction process R10 by depending on the self pressure.
The high boiling point solvent oil hydrogenation stabilization reaction process R30 can be arranged or jointly arranged to produce the high boiling point hydrogen donor HBDS, and hydrocarbon components with the conventional boiling points of 200-530 ℃ from the high boiling point oil R10P-HS-L are processed.
Therefore, the first purpose of the invention is to propose a method for oil-coal co-refining by using short-cycle hydrogen-supplying solvent oil.
The invention aims to provide a method for co-refining oil and coal by using short-cycle hydrogen-supplying solvent oil, which is a combined method of a front-mounted solvent oil hydrogenation stabilization reaction process R30 and an oil and coal co-refining hydrogenation reaction process R10.
The third purpose of the invention is to provide an oil-coal co-refining method for injecting hydrogen donor solvent in batches and in a classified manner by using short-circulation hydrogen donor solvent oil.
The fourth purpose of the invention is to provide an oil-coal co-refining method using short-cycle hydrogen-supplying solvent oil, which can be used in combination with various direct oil-making reaction methods by coal hydrogenation.
Disclosure of Invention
The invention relates to an oil-coal co-refining method using short-cycle hydrogen supply solvent oil, which is characterized by comprising the following steps:
(1) in the oil-coal slurry preparation process M10, raw oil SHVGO of non-coal derived oil and coal powder SF are prepared into oil-coal slurry R10F;
(2) in the oil-coal co-refining hydrogenation reaction process R10, under the condition that short-process circulating solvent oil SR-DS from the step (4), hydrogen and possibly used oil-coal co-refining hydrogenation catalysts exist, the oil-coal slurry R10F is converted into a coal co-refining hydrogenation product R10P;
in the oil-coal co-refining hydrogenation reaction process R10, coal liquefaction reactions including swelling, pyrolysis, hydrocracking and hydrogenation stabilization are carried out on coal powder in the oil-coal slurry R10F, light-weight reactions including thermal cracking and hydrogenation stabilization are carried out on raw oil SHVGO in the oil-coal slurry R10F, and the short-process circulating solvent oil SR-DS has at least the function of releasing active hydrogen for pyrolysis free radicals;
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the short-process cycle solvent oil hydrogenation modification reaction process R30, under the conditions of hydrogen and a short-process cycle solvent oil hydrogenation catalyst, at least part of hydrogen-donating hydrocarbon precursors R30F containing hydrocarbon components in hot high-gas R10P-HS-V undergo partial saturation reaction of aromatic hydrocarbon hydrogenation to be converted into reaction effluents R30P rich in hydrogen-donating hydrocarbon;
the high-pressure material flow containing hydrocarbon components in the reaction effluent R30P is used as short-process circulating solvent oil SR-DS and enters an oil-coal co-refining hydrogenation reaction process R10;
a high-pressure gas stream comprising hydrogen from hot high-pressure gas R10P-HS-V is used as hydrogen-rich stream XH;
(5) separating and recovering hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in the post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV is returned to the hydrogenation reaction process for recycling.
The invention discloses a 1 st flow mode of a short-flow cycle solvent oil hydrogenation modification process R30-UNIT, which comprises the following steps:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a post-positioned online hydrogenation modification method, hot high-pressure gas R10P-HS-V directly enters a reaction process R30, a hot high-pressure separation process R30P-HS and a transfer PUMP A-PUMP of a hydrogenation modification reaction process R30 of the short-process circulating solvent and a product R30P of the R30 are arranged, and the method comprises the following steps:
① in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the hot high-pressure gas R10P-HS-V enters the reaction process R30 and is converted into a product R30P rich in hydrogen supply hydrocarbon, and hydrocarbon components carried by the hot high-pressure gas R10P-HS-V are subjected to at least partial aromatic hydrogenation saturation reaction;
② is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in the hot high-pressure separation process R30P-HS, the product R30P, at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH, and at least one part of the hot high-pressure oil R30P-HS-L is pressurized by a delivery PUMP A-PUMP and then used as material flow SR-DS to enter the oil-coal co-refining hydrogenation process R10.
The invention discloses a 2 nd flow mode of a short-flow cycle solvent oil hydrogenation modification process R30-UNIT, which comprises the following steps:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the process mode is a post-positioned online hydrogenation modification method, the hot high-temperature oil R10P-HS-V-MS-L obtained by separating hot high-temperature gas R10P-HS-V in the temperature and high-pressure separation process R10P-HS-V-MS enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, the temperature and high-pressure separation process R10P-HS-V-MS, the hydrogenation modification reaction process R30 for preparing the short-process cycle solvent, the heat and high-pressure separation process R30P-HS for R30 product R30P, and the delivery PUMP A-PUMP are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V into high-temperature high-pressure gas R10P-HS-V-MS-V and high-temperature high-pressure oil R10P-HS-V-MS-L in the high-temperature high-pressure separation process R10P-HS-V-MS;
at least a portion of the hot high partial gas R30P-HS-V is used as stream XH;
② in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the high temperature and high temperature separation oil R10P-HS-V-MS-L enters the reaction process R30 and is converted into a product R30P rich in hydrogen supply hydrocarbon, and hydrocarbon components carried by the high temperature and high temperature separation gas R10P-HS-V are subjected to at least partial aromatic hydrogenation partial saturation reaction;
③ is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in the hot high-pressure separation process R30P-HS, the product R30P, at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH, and at least one part of the hot high-pressure oil R30P-HS-L is pressurized by a delivery PUMP A-PUMP and then used as material flow SR-DS to enter the oil-coal co-refining hydrogenation process R10.
In the invention, the 3 rd flow mode of the short-flow cycle solvent oil hydrogenation modification process R30-UNIT is as follows:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F pressure-increasing material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon;
④ in the thermal high pressure separation process R30P-HS, the product R30P is separated into thermal high-pressure gas R30P-HS-V and thermal high-pressure oil R30P-HS-L, at least a part of thermal high-pressure oil R30P-HS-L is used as material flow SR-DS to enter into the oil-coal co-refining hydrogenation process R10.
The invention discloses a 4 th flow mode of a short-flow cycle solvent oil hydrogenation modification process R30-UNIT, which comprises the following steps:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F of the pressurized material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon, at least a part of hot high-fraction oil R30P-HS-L is used as the material flow SR-DS to enter the oil-coal co-refining hydrogenation reaction process R10.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the thermal high-pressure separation process R30P-HS, stripping hydrogen R30P-HS-BV can be used to contact liquid existing in the thermal high-pressure separation process R30P-HS so as to strip low boiling point components in the liquid, and stripping gas enters the thermal high-pressure gas R30P-HS-V.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, in the thermal high-pressure separation process R30P-HS, the thermal high-pressure separation oil R30P-HS-L is mainly composed of hydrocarbons with a conventional boiling point higher than 280 ℃ or higher than 230 ℃.
The invention (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and the thermal high-pressure separation process R30P-HS operating temperature: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the temperature and pressure separation process R10P-HS-V-MS, the stripping hydrogen R10P-HS-V-MS-BV can be used to contact the liquid existing in the temperature and pressure separation process R10P-HS-V-MS so as to strip the low boiling point components in the liquid, and the stripping gas can finally enter the temperature and pressure separation gas R10P-HS-V-MS-V.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, in the temperature and high pressure separation process R10P-HS-V-MS, the temperature and high-pressure separation oil R10P-HS-V-MS-L mainly comprises hydrocarbons with the conventional boiling point higher than 250 ℃ or higher than 200 ℃.
The invention (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the temperature and pressure separation process R10P-HS-V-MS operating temperature: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
The invention relates to a method for preparing coal oil slurry, which comprises the following steps of (1) in the coal oil slurry preparation process M10, coal slurry R10F, mass concentration of coal powder: typically greater than 30%, typically greater than 40%, and most preferably greater than 45%.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, a pre-hydrogenation reaction section R10-DD can be arranged;
in the pre-hydrogenation reaction section R10-DD, the oil coal slurry R10F is subjected to pre-hydrogenation reaction and is converted into a coal pre-hydrogenation product R10-DD-P, and the short-process hydrogen supply solvent SR-DS plays a role in providing active hydrogen and generally plays a main role in providing the active hydrogen; generally, the ratio of the standard state volume of the hydrogen to the volume of the oil coal slurry in the pre-hydrogenation reaction section R10-DD is lower than 300: 1, so that the gasification rate of the short-flow hydrogen supply solvent SR-DS is reduced.
In the invention, (2) at least 1 intermediate product gas-liquid separation step R10-MS and at least 2 liquid stream material coal hydrogenation oil-making reaction areas which are operated in series can be arranged in the oil-coal co-refining hydrogenation reaction process R10;
at least one part of the liquid-phase-containing material discharged from the gas-liquid separation step R10-MS enters a downstream liquid stream material coal hydrogenation oil-making reaction zone;
at least a part of the gas-phase-containing material discharged from the gas-liquid separation step R10-MS does not enter a downstream liquid stream material coal hydrogenation oil-making reaction zone.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, based on the liquid stream material coal hydrogenation oil-making reaction process, hydrogen-supplying solvent can be injected in batches, namely at least 2 hydrogen-supplying hydrocarbon stream adding points are used, the first hydrogen-supplying hydrocarbon stream adding point is the initial reaction zone of the oil-coal co-refining hydrogenation reaction process R10, and the second hydrogen-supplying hydrocarbon stream adding point is positioned at the downstream of the first hydrogen-supplying hydrocarbon stream adding point.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, based on the liquid stream material coal hydrogenation oil-making reaction process, hydrogen-supplying solvents can be injected in a classified mode, namely at least 2 hydrogen-supplying hydrocarbon stream adding points are used, and a second hydrogen-supplying hydrocarbon stream adding point mainly composed of normal hydrocarbons with higher boiling points is positioned at the downstream of a first hydrogen-supplying hydrocarbon stream adding point mainly composed of normal hydrocarbons with lower boiling points.
In the invention, (3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
in the hot high pressure separation process R10P-HS, stripping hydrogen R10P-HS-BV can be used to contact liquid existing in the hot high pressure separation process R10P-HS to strip low boiling components therein; generally, the stripping gas finally enters into the hot high-pressure gas R10P-HS-V.
In the invention, (3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
typically, the hot high-molecular gas R10P-HS-V, wherein the hydrocarbons consist essentially of hydrocarbons with a conventional boiling point below 450 ℃;
generally, the hot high-molecular gas R10P-HS-V, wherein the hydrocarbon mainly comprises hydrocarbon with a conventional boiling point lower than 400 ℃;
it is possible to use hot high-molecular gases R10P-HS-V, in which the hydrocarbons consist essentially of hydrocarbons with a conventional boiling point below 350 ℃.
In the invention, (5) separating and recovering hot hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in a post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV returns to the hydrogenation reaction process for recycling, and the hydrogen volume concentration of the hydrogen-rich gas XHV is: generally greater than 70%, generally greater than 80%, preferably greater than 90%; usually, at least a part of the hydrogen-rich gas XHV is returned to the hydrogenation reaction process after purifying the hydrogen for recycling.
According to the invention, (6) in a separation/fractionation part R10P-HS-L-DS, separating hot high-grade oil R10P-HS-L to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃ or above 530 ℃;
and (3) according to the requirement, taking a part of the liquefaction residue VS as a recycle raffinate VSR to enter the oil-coal co-refining hydrogenation reaction process R10.
According to the invention, (6) in a separation/fractionation part R10P-HS-L-DS, separating hot high-grade oil R10P-HS-L to obtain liquefied product distillate oil and liquefied residue VS;
part of the liquefaction residue VS is used as a product VSP, and part of the liquefaction residue is used as a liquefaction residue circulating material VSR to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10, for example, the liquefaction residue circulating material VSR is used as a coal slurry preparation solvent oil to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through an oil-coal slurry preparation process M10.
In the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursor processed can be 1-path or 2-path or multi-path material.
In the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursor processed can be 2-path or multi-path material, and a synchronous hydrogenation mode of mixed raw material hydrocarbon is adopted.
In the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursors processed can be 2 hydrogen-donating hydrocarbon precursors, the boiling ranges and the molecular structures of the 2 hydrogen-donating hydrocarbon precursors have larger difference, and the 2 hydrocarbon streams adopt asynchronous hydrogenation modes selected from 1 or more of the following methods:
① the first hydrogen donor hydrocarbon precursor is hydrogenated after being mixed with the second hydrogen donor hydrocarbon precursor;
② the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel to obtain a product, mixed and separated;
③ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel, and the obtained products are mixed and then hydrogenated again;
④ the first hydrogen-supplying hydrocarbon precursor and the second hydrogen-supplying hydrocarbon precursor are hydrogenated respectively, the products are separated under high pressure, at least one part of each high-pressure oil enters into the oil coal co-refining hydrogenation process R10.
The invention may comprise the steps of:
(6) separating hot high-fraction oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil with a conventional boiling point of 250-530 ℃ and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
(7) in the process of the solvent oil hydrogenation reaction R20, under the condition of hydrogen and a solvent oil hydrogenation catalyst, at least part of the aromatic hydrocarbon hydrogenation partial saturation reaction of the hydrogen-donating hydrocarbon precursor R20F is carried out to be converted into reaction effluent R20P rich in hydrogen-donating hydrocarbon;
a hydrogen-donating hydrocarbon precursor R20F comprising at least a portion of distillate oil ML;
in the solvent oil hydrogenation reaction process R20, the hydrogen donor hydrocarbon precursor is processed into 1-way or 2-way or multi-way material.
(8) Separating the reaction effluent R20P to obtain a long-process circulating hydrogen donor solvent LR-DS;
at least a part of the hydrogen donor solvent LR-DS enters the oil-coal co-refining hydrogenation reaction process R10.
In the invention, (7) in the solvent oil hydrogenation reaction process R20, the processed hydrogen-donating hydrocarbon precursor is 2-way or multi-way material, and a synchronous hydrogenation mode of mixed raw material hydrocarbon can be adopted.
In the invention, (7) in the solvent oil hydrogenation reaction process R20, the processed hydrogen-donating hydrocarbon precursors are 2 hydrogen-donating hydrocarbon precursors, and the boiling ranges and molecular structures of the 2 hydrogen-donating hydrocarbon precursors have large differences, and the asynchronous hydrogenation mode adopted by the 2 hydrocarbon streams can be selected from 1 or more of the following methods:
① the first hydrogen donor hydrocarbon precursor is hydrogenated after being mixed with the second hydrogen donor hydrocarbon precursor;
② the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel to obtain a product, mixed and separated;
③ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel, and the obtained products are mixed and then hydrogenated again;
④ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are hydrogenated respectively to obtain products, which are separated under high pressure, at least part of each high-pressure oil is mixed and then enters the separation/fractionation part LR-DSF.
In the invention, (2) the operation mode of the reactor used in the oil-coal co-refining hydrogenation reaction process R10 can be selected from 1 or a combination of several of the following:
① suspension bed is slurry bed;
② bubbling bed;
③ micro-expanded bed.
In the invention, (4) the hydrogenation reactor used in the short-process cycle solvent oil hydrogenation modification process R30-UNIT can be operated in a mode selected from 1 or a combination of several of the following modes:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
In the present invention, (7) the reactor used in the solvent oil hydrogenation reaction process R20 may be operated in a manner selected from 1 or a combination of several of the following:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
In general, the invention (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point of the hydrocarbons with the boiling point higher than 250 ℃ in the short-process cycle solvent oil SR-DS: the weight content of the partially saturated aromatic hydrocarbon is more than 15%, and the aromatic carbon rate is 0.35-0.70;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 15 percent, and the aromatic carbon rate is 0.35-0.70.
The invention, generally, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point of the hydrocarbons with the temperature higher than 250 ℃ in the short-process cycle solvent oil SR-DS: the weight content of the partially saturated aromatic hydrocarbon is more than 20 percent, and the aromatic carbon rate is 0.40-0.65;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 20 percent, and the aromatic carbon rate is 0.40-0.65.
The invention, preferably, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point of the short-process cycle solvent oil SR-DS is higher than 250 ℃ hydrocarbon: the weight content of the partially saturated aromatic hydrocarbon is more than 25%, and the aromatic carbon rate is 0.45-0.60;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 25 percent, and the aromatic carbon rate is 0.45-0.60.
In the invention, the operation conditions of the solvent oil hydrogenation reaction process are generally as follows:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W series hydrogenation catalyst; the reaction temperature is 300-390 ℃, the hydrogenation pressure is 10-25 MPa, and the gas-liquid volume ratio is 300-1000 NL/kg;
(7) in the solvent oil hydrogenation reaction process R20, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W hydrogenation catalyst; the reaction temperature is 300-390 ℃, the hydrogenation pressure is 10-25 MPa, and the gas-liquid volume ratio is 300-1000 NL/kg.
In the invention, the operation conditions of R10 in the oil-coal co-refining hydrogenation reaction process are as follows:
(2) in the oil-coal co-refining hydrogenation reaction process R10, the reaction temperature is 400-465 ℃, the reactor pressure is 6-30 MPa, the gas-liquid volume ratio is 600-1500 NL/kg, the addition amount of the liquefaction catalyst is 0.5-3 mass% of the weight of the dry coal powder, the addition amount of the cocatalyst is 1.0-2.0 of the molar ratio of S in the cocatalyst to the active metal of the catalyst, and the solid concentration of coal slurry is 45-50 mass%.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, the hydrogenation catalyst which can be used is a composite hydrogenation catalyst and comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the catalyst R10C is less than 2 wt%; R10C is a powdery particle having a particle diameter of 1 to 100 μm.
According to the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, the coal hydrogenation direct liquefaction catalyst can be a nano ultrafine particle hydrated iron oxide catalyst and/or iron oxide and/or pyrite and/or hematite and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
The invention, generally, (2) in the oil coal co-refining hydrogenation reaction process R10, using fresh hydrogen and/or recycle hydrogen;
(4) in the short-flow cycle solvent oil hydrogenation modification reaction process R30, using new hydrogen and/or cycle hydrogen;
(7) fresh hydrogen and/or recycle hydrogen is used in the solvent oil hydrogenation process R20.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 1 st flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 2 nd flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through the oil-coal slurry preparation process M10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 3 rd flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 in the oil-coal slurry preparation process M10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 4 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydrogenation modification process CR10UNIT, and the CSH returns to an oil-coal co-refining hydrogenation reaction process R10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 5 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydro-upgrading process, and the CSH is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through an oil-coal slurry preparation process M10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 6 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the deasphalted distilled oil CFD obtained by the separation step of the pyrolysis tar CF, the high-pressure system of the hydrogenation modification process CR10UNIT of the CFD and the high-pressure system of the hydrogenation stabilization reaction process R20 of the solvent oil are partially or completely shared.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residues VS, and the 7 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the deasphalted distilled oil CFD obtained by the separation step of the pyrolysis tar CF, a high-pressure system of a hydrogenation upgrading process CR10UNIT of the CFD and a high-pressure system of a hydrogenation stable reaction process R30 of the short-flow hydrogen supply solvent oil are partially or completely shared.
In the invention, (1) in the process of preparing the oil-coal slurry, M10, raw oil SHVGO is non-coal derived oil and mainly consists of hydrocarbon with the conventional boiling point higher than 530 ℃.
Drawings
FIG. 1 is a schematic diagram of the principle process of the oil-coal co-refining method using short-cycle hydrogen-supplying solvent oil according to the present invention, which includes a coal-oil slurry preparation process M10, a coal-oil co-refining hydrogenation reaction process R10, a liquefied product thermal high-pressure separation process R10P-HS, a separation/fractionation section R10P-HS-L-DS of thermal high-purity oil R10P-HS-L, a thermal high-purity gas R10P-HS-V post-treatment system R10P-HS-V-AUNIT, a long-process cycle solvent hydrogenation modification reaction process R20, a product thermal high-pressure separation process R20P-HS of R20, a separation/fractionation section LR-F of thermal high-purity oil R20P-HS-L, a liquefied raffinate fluidized pyrolysis reverse process BR10UNIT, a distillation process CFDS of pyrolysis tar CF, and a hydrogenation modification process CR10UNIT of distillation oil CFD of pyrolysis tar CF.
As with the flow shown in fig. 1, some processes or units may or may not be used as desired for a particular manufacturing process.
As shown in figure 1, the invention sets up a short-flow cycle solvent hydrogenation modification process R30-UNIT prepared by utilizing hydrocarbon components in hot high-pressure gas R10P-HS-V, which is different from the conventional oil-coal co-refining process.
As shown in fig. 1, according to the requirement, precursor hydrocarbon R20F of long-run hydrogen-supplying solvent LR-DS may be used, and enters the solvent oil hydrogenation stabilization reaction process R20 through a pipeline 151, and in the presence of hydrogen and long-run solvent oil hydrogenation stabilization catalyst, aromatic hydrogenation partial saturation reaction occurs, and the product is converted into product R20P rich in hydrogen-supplying hydrocarbon, and the product R20P is separated to obtain hydrocarbon liquid stream LS-DS rich in hydrogen-supplying hydrocarbon, which is used as solvent oil for preparing coal oil slurry with pulverized coal SF.
As shown in FIG. 1, the recycle raffinate VSR may be fed to the coal slurry preparation process M10 via a pipe 1451 and then added to the coal slurry R10F as required.
As shown in figure 1, the solvent oil hydrogenation reaction product R20P enters a thermal high-pressure separation process R20P-HS through a pipeline 155 and is separated into thermal high-pressure gas R20P-HS-V and thermal high-pressure oil R20P-HS-L.
R20P-HS-V contains most of hydrogen and part of low boiling point hydrocarbon in R20P, and R20P-HS-V can be recovered in various ways, such as separation into hydrocarbon oil and recycling of hydrogen-rich gas.
When the pressure of R20P-HS-V is higher than the operating pressure of R10 in the oil-coal co-refining hydrogenation reaction process, at least a part of hot high-molecular gas R20P-HS-V can be used secondarily. As shown in fig. 1, the mixture enters the oil-coal co-refining hydrogenation reaction process R10 through a pipe 165, for example, the mixture is used as the inlet hydrogen of the first reactor of the oil-coal co-refining hydrogenation reaction process R10, and hydrogen is added at the inlet of the rear reactor, for example, the mixture is used as the cooling hydrogen, the flushing hydrogen and the stripping hydrogen of the oil-coal co-refining hydrogenation reaction process R10; the residual hot high-pressure gas R20P-HS-V can be used as stripping gas of the hot high-pressure process R10P-HS, or can be mixed with a gas phase stream based on R10P for treatment.
As shown in FIG. 1, the hot high-boiling oil R20P-HS-L contains part of the low-boiling-point hydrocarbons and most of the high-boiling-point hydrocarbons in R20P, and at least a part of the hot high-boiling-point oil R20P-HS-L enters the separation/fractionation part LR-DSF through a pipeline 166 to separate out the long-flow circulation hydrogen-supplying solvent LR-DS.
As shown in fig. 1, the blending coal powder SF enters an oil-coal slurry preparation process M10 through a pipeline 101, the raw material oil SHVGO enters an oil-coal slurry preparation process M10 through a pipeline 102, the long-flow circulating hydrogen-donor solvent LR-DS enters an oil-coal slurry preparation process M10 through a pipeline 175, and the oil-coal slurry obtained by M10 is used as a raw material R10F of an oil-coal co-refining hydrogenation reaction process R10; if necessary, in the coal oil slurry preparation process M10, a coal hydrogenation oil catalyst, a vulcanizing agent, and the like may be added to the coal oil slurry R10F.
The raw oil SHVGO is non-coal derived oil.
As shown in fig. 1, all the coal oil slurry R10F enters the coal oil co-refining hydrogenation process R10 through the pipeline 111, coal liquefaction hydrogenation reactions such as coal swelling, pyrolysis, hydrocracking, hydrogenation stabilization and the like occur in the presence of hydrogen and a possibly used coal oil co-refining hydrogenation catalyst, reactions such as hydrogenation saturation of possibly existing raffinate VSR, hydrogenation impurity removal hydrogenolysis, hydrocracking and the like occur simultaneously, the short-cycle hydrogen supply solvent SR-DS plays a hydrogen supply role, and a dehydrogenation product of hydrogen supply hydrocarbon can be re-hydrogenated and converted into hydrogen supply hydrocarbon to be repeatedly hydrogenated, i.e., plays a role in transferring active hydrogen.
As shown in figure 1, all the oil-coal slurry R10F enters the oil-coal co-refining hydrogenation reaction process R10 and is converted into a coal hydrogenation oil product R10P, and the product R10P enters the thermal high-pressure separation process R10P-HS through a pipeline 121 and is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L.
As shown in FIG. 1, R10P-HS-V conveyed by the pipeline 131 contains most of hydrogen and part of low boiling point hydrocarbon in R10P, and the hot high-molecular gas R10P-HS-V is subjected to a short-flow circulation hydrogen supply solvent hydrogenation modification process R30-UNIT to generate a short-flow circulation hydrogen supply solvent SR-DS and hydrogen-rich gas XH.
As shown in FIG. 1, the hydrogen-rich gas XH is introduced into the post-treatment system R10P-HS-V-AUNIT through the pipe 341, and the hot hydrogen-rich gas XH is separated and recovered to obtain the hydrogen-rich gas XHV and usually the hydrocarbon oil XHL discharged through the pipe.
The post-treatment system R10P-HS-V-AUNIT generally includes at least processes of cooling, water injection washing, gas-liquid separation, gas-oil-water three-phase separation, etc. of the hydrogen-rich gas XH, and aims to obtain the hydrogen-rich gas that can be recycled and recover hydrocarbons in the hydrogen-rich gas XH, and the operating temperature of the gas-liquid separation or gas-oil-water three-phase separation process is as follows: usually 10 to 80 ℃, usually 20 to 70 ℃, preferably 30 to 55 ℃.
Usually, at least a part of the hydrogen-rich gas XHV is returned to the hydrogenation process for recycling, as shown in FIG. 1, a part of the hydrogen-rich gas XHV can be returned to the oil-coal blending hydrogenation reaction process R10 for recycling as RH01 through a pipeline 195, a part of the hydrogen-rich gas XHV can be returned to the solvent oil hydrogenation stabilization reaction process R20 for recycling as RH02 through a pipeline,
as shown in figure 1, fresh hydrogen FH is conveyed through a pipeline 250, one FH01 path can enter the oil coal co-refining hydrogenation reaction process R10 through a pipeline 251 and be used for chemical hydrogen consumption and the like, and the other FH02 path can enter the circulating solvent hydrogenation modification reaction process R20 through a pipeline 252 and be used for chemical hydrogen consumption and the like.
As shown in figure 1, the hot high-fraction oil R10P-HS-L enters a separation/fractionation part R10P-HS-L-DS of the hot high-fraction oil R10P-HS-L through a pipeline 132 to separate gas, liquefied product distillate oil ML and liquefied residue VS.
Typically, the partially liquefied product fraction oil ML is passed as product TP1 via line 148 to downstream processing steps, and the partially liquefied product fraction oil ML can be passed as hydrogen donor precursor R20F-a via line 143 to the solvent oil hydrogenation stabilization reaction process R20, as desired.
As shown in FIG. 1, at least a portion of the liquefaction residue VS is typically passed as product VSP via line 1452 to downstream processing steps such as to a fluidized pyrolysis process BR10UNIT for liquefied raffinate, which serves to discharge solid waste, and may be fed as recycle VSR via line 1451 to the coal slurry preparation process M10 for blending into the coal slurry R10F, as desired.
The oil coal co-refining hydrogenation reaction process R10 produces oil coal co-refining hydrogenation to generate oil R10P-0, usually, the bottom of a vacuum distillation tower used by a separation part R10P-HS-L-DS of hot high-molecular oil R10P-HS-L is provided with solid-liquid material VS at the bottom of the vacuum distillation tower mainly consisting of hydrocarbon components with the conventional boiling point higher than 500-540 ℃ and solids, namely, raffinate, the solid-liquid material VS at the bottom of the vacuum distillation tower can be returned to the oil coal co-refining hydrogenation reaction process R10 as cycle material VSR to repeatedly utilize part of catalyst particles and deeply convert part of heavy hydrocarbons (colloid, asphaltene and preasphaltene) for many times, and simultaneously the solid-liquid material VS at the bottom of the vacuum distillation tower is discharged as raffinate product VSP to discharge waste catalyst particles and coal skeleton particles which can not be liquefied, and the heavy hydrocarbons such as oil, colloid, asphaltene and preasphaltene are carried in the raffinate, the softening point of the raffinate VS is usually above 100 to 150 ℃.
The VSR returning to the circulating raffinate VSR of the R10 in the oil-coal co-refining hydrogenation reaction process contains the waste catalyst particles which cannot be liquefied and the coal-carbon skeleton particles which cannot be liquefied, and simultaneously, part of the heavy hydrocarbons carried by the VSR are polycyclic aromatic hydrocarbons, colloids, asphaltene and preasphaltene which are difficult to be hydrogenated and lightened, so that the existence of the VSR in the circulating feed remarkably worsens the operating conditions of the R10 in the oil-coal co-refining hydrogenation reaction process and related systems, shortens the continuous operation period, and limits or compresses the range of raw coal types (mainly provides upper limit requirements on the ash content and the inert component content of pulverized coal).
As shown in figure 1, the invention forms a short circulation flow path of light solvent oil for an oil-coal co-refining hydrogenation reaction process R10.
As shown in FIG. 1, the hydrogenation stabilization reaction process of solvent oil R20 can be set according to the needs, distillate oil R20F-A from the pipeline 143, distillate oil R20F-B with proper boiling range and discharged from R10P-HS-V-AUNIT through the pipeline, such as warm high-temperature distillate oil obtained from the warm high-temperature separation process, and other proper distillate oil can be processed.
The solvent oil hydrogenation stabilizing reaction process R20 can process 2 or more hydrogen-donating hydrocarbon precursors, and can adopt a synchronous hydrogenation mode of mixed raw material hydrocarbon.
In the solvent oil hydrogenation stabilization reaction process R20, when the boiling ranges and molecular structures of the processed 2 hydrogen-donating hydrocarbon precursors are possibly different greatly, the 2 hydrocarbon streams can adopt an asynchronous hydrogenation mode, for example, a prehydrogenation product obtained by prehydrogenating the distillate oil R20F-A and the distillate oil R20F-B are mixed and then are hydrogenated together; for example, the fraction oil R20F-B is hydrogenated after being mixed with the fraction oil R20F-A after being pre-hydrogenated; for example, distillate R20F-A and distillate R20F-B are respectively hydrogenated in parallel, and the obtained products are mixed and separated; for example, distillate R20F-A and distillate R20F-B are respectively hydrogenated in parallel, and the obtained products are mixed and hydrogenated again; for example, the products obtained after the distillate R20F-A and the distillate R20F-B are respectively hydrogenated are respectively subjected to thermal high-pressure separation, and at least one part of each thermal high-pressure gas enters the oil-coal co-refining hydrogenation reaction process R10.
As shown in figure 1, the solvent oil hydrogenation stabilizing reaction process R20 can process 2 or more hydrogen-donating hydrocarbon precursors in a set of high-pressure systems, so that the investment and the energy consumption are low.
As shown in FIG. 1, the invention sets up a short-flow cycle solvent hydro-modification process R30-UNIT using hydrocarbon components in hot high-pressure gas R10P-HS-V, with the overall objective of:
① preparing short-process circulating hydrogen supply solvent SR-DS by using hydrocarbon components in hot high-pressure gas R10P-HS-V;
② recovering the hydrogen and other components in the hot high-pressure gas R10P-HS-V which do not enter the short-process circulating solvent hydrogenation modification process R30-UNIT or do not enter the short-process circulating solvent, and the component flow XH enters the post-treatment system R10P-HS-V-AUNIT through the pipeline 341.
As shown in fig. 1, in the short-run recycle solvent hydro-modification process R30-UNIT, a feed XF such as fresh hydrogen or recycle hydrogen stream or gaseous hydrogen, delivered via line 315, may be used as desired, possibly producing a product XP such as a hydrogen-containing and/or hydrocarbon-containing product, delivered via line 320, as desired for the actual run.
FIG. 2 is a schematic diagram of the principle process of the first technical scheme of the invention, namely R30-UNIT for preparing short-process hydrogen-supplying hydrocarbon by using hydrocarbon oil in hot high-gas R10P-HS-V, in the oil-coal co-refining method of short-cycle hydrogen-supplying solvent oil, and the method is a post-positioned online hydrogenation stabilization method for directly feeding hot high-gas R10P-HS-V into a reaction process R30, and comprises a hot high-pressure separation process R30P-HS and a delivery PUMP A-PUMP for preparing a hydrogenation modification reaction process R30 of short-process cycle solvent and a product R30P of R30.
As shown in figure 2, a precursor of the short-process hydrogen supply solvent SR-DS is hydrocarbon in hot high-molecular gas R10P-HS-V, the hot high-molecular gas R10P-HS-V enters a short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 through a pipeline 131, an aromatic hydrocarbon hydrogenation partial saturation reaction is carried out in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the aromatic hydrocarbon hydrogenation partial saturation reaction is converted into a product R30P rich in hydrogen supply hydrocarbon, the product R30P is separated to obtain a hydrocarbon liquid stream SR-DS rich in hydrogen supply hydrocarbon, and the hydrocarbon liquid stream SR-DS enters an oil-coal co-refining hydrogenation reaction process R10.
As shown in FIG. 2, the product R30P enters a thermal high-pressure separation process R30P-HS through a pipeline 311 and is separated into thermal high-pressure gas R30P-HS-V and thermal high-pressure oil R30P-HS-L, the thermal high-pressure gas R30P-HS-V is used as a material flow XH, and the thermal high-pressure oil R30P-HS-L is used as a material flow SR-DS.
As shown in FIG. 2, any suitable operating conditions may be used for the thermal high pressure separation process R30P-HS for the purpose of obtaining hydrogen donating hydrocarbons and separating out gases consisting of other components. Usually the hot high-oil R30P-HS-L is mainly composed of hydrocarbons with conventional boiling point higher than 280 ℃ or higher than 230 ℃, the operating temperature of the gas-liquid separation process is: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
As shown in FIG. 2, hot high-molecular gas R10P-HS-V directly enters into reaction process R30, therefore, the operation pressure of hot high-molecular oil R30P-HS-L is lower than that of oil-coal co-refining hydrogenation process R10, and hot high-molecular oil R30P-HS-L enters into PUMP A-PUMP via pipe 351 to be pressurized and then enters into oil-coal co-refining hydrogenation process R10 via pipe 352 to be used as material flow SR-DS.
As shown in FIG. 2, the hot high pressure separation process R30P-HS may be contacted with stripping hydrogen R30P-HS-BV via line 3158 with the liquid present in the hot high pressure separation process R30P-HS to strip the lower boiling components therefrom, as desired, which may ultimately be passed into the hot high partial gas R30P-HS-V.
With respect to the scheme shown in FIG. 2, there are advantages in that hydrogen is reused and the process is simple, and there is a disadvantage in that the impurity gas such as H of the hot high-split gas R10P-HS-V cannot be avoided2O、NH3、CO、CO2The introduction of HCl, R30, these impurity gases severely worsen the R30 catalyst operating performance (resulting in short catalyst life for R30 and unstable quality of hydrogen donor solvent).
In order to overcome the defects of the scheme shown in the figure 2, the flow of a temperature and high pressure separation process R10P-HS-V-MS provided with hot high-pressure gas R10P-HS-V shown in the figure 3 is provided, the hot high-pressure gas R10P-HS-V is separated into the temperature and high-pressure gas R10P-HS-V-MS-V and the temperature and high-pressure oil R10P-HS-V-MS-L in the temperature and high pressure separation process R10P-HS-V-MS-L, and the temperature and high-pressure oil R10P-HS-V-MS-L enters a short-flow hydrogen supply solvent oil hydrogenation stabilization reaction process R30.
FIG. 3 is a schematic diagram of the principle process of the 2 nd technical scheme of preparing a short-process hydrogen supply hydrocarbon part R30-UNIT from hydrocarbon oil in hot high-pressure gas R10P-HS-V according to the oil-coal co-refining method of short-cycle hydrogen supply solvent oil of the present invention, and compared with the scheme shown in FIG. 2, the method adds a temperature and pressure separation process R10P-HS-V-MS of hot high-pressure gas R10P-HS-V, and is a post-positioned online hydrogenation stabilization method of entering the temperature and pressure separation process R10P-HS-V-MS-L into a short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, and comprises a temperature and pressure separation process R10P-HS-V-MS, a hydrogenation modification reaction process R30 for preparing a short-process cycle solvent, a heat and pressure separation process R30P-HS and a delivery PUMP A-PUMP of R30 product R30P.
As shown in FIG. 3, the hot high-pressure gas R10P-HS-V enters a high-temperature high-pressure separation process R10P-HS-V-MS through a pipeline 131, and is separated into high-temperature high-pressure gas R10P-HS-V-MS-V and high-temperature high-pressure oil R10P-HS-V-MS-L, the high-temperature high-pressure oil R10P-HS-V-MS-L enters a short-flow hydrogen supply solvent oil hydrogenation stabilization reaction process R30 through a pipeline 305, and the hot high-pressure gas R30P-HS-V is used as a material flow XH.
As shown in FIG. 3, the temperature and pressure separation process R10P-HS-V-MS may use stripping hydrogen R10P-HS-V-MS-BV delivered via conduit 3151 to contact the liquid present in the temperature and pressure separation process R10P-HS-V-MS to strip the low boiling components therefrom, and the stripping gas may finally enter the temperature and pressure separation process R10P-HS-V-MS-V, as desired.
As shown in FIG. 3, the warm high pressure separation process R10P-HS-V-MS, the purpose of which is to obtain a hydrogen donor hydrocarbon precursor and separate out a gas consisting of other components, may use any suitable operating conditions. Introducing normal-temperature high-separation oil R10P-HS-V-MS-L which mainly comprises hydrocarbons with the conventional boiling point higher than 250 ℃ or higher than 200 ℃, wherein the operation temperature of the gas-liquid separation process of the high-temperature high-pressure separation process R10P-HS-V-MS is as follows: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
With respect to the solution shown in FIG. 3, it is advantageous to avoid the impurity gases such as H from the hot high-split gas R10P-HS-V2O、NH3、CO、CO2The HCl enters into the reaction process R30, and the disadvantage is that hydrogen cannot be reused, so the hydrogen system has complex flow and large investment.
In order to overcome the defects of the scheme shown in fig. 3, the scheme shown in fig. 4 and fig. 5 is provided, under the premise of setting a temperature and pressure separation process R10P-HS-V-MS of hot high-temperature gas R10P-HS-V, the position of a booster pump on a circulation route of a short-flow hydrogen supply solvent is adjusted to be a booster pump of temperature and high-temperature oil R10P-HS-V-MS-L, so that the operating pressure of the heat and pressure separation process R30P-HS of a product R30P of a reaction process R30 and R30 can be increased to be higher than that of the oil-coal co-refining hydrogenation process R10, and conditions are created for enabling the hot high-temperature gas-liquid flow of the R30P or R30P to enter the oil-coal co-refining hydrogenation process R10 by virtue of self pressure, so that hydrogen in a reaction product R30P can be secondarily used as required, such as entering the oil-coal co-refining hydrogenation process R10.
FIG. 4 is a schematic diagram of the principle process of the 3 rd technical scheme of preparing a short-process hydrogen-donating hydrocarbon part R30-UNIT from hydrocarbon oil in hot high-pressure gas R10P-HS-V in the oil-coal co-refining method of the short-cycle hydrogen-donating solvent oil of the present invention, compared with the scheme shown in FIG. 3, the booster PUMP A-PUMP of the short-process hydrogen-donating solvent is cancelled in the process, the warm high-pressure oil R10P-HS-V-MS-LB-PUNP booster PUMP is added, the operating pressure of the hot high-pressure separation process R30P-HS of the R30P product R30 and R30 in the reaction process is increased to be higher than the operating pressure of the R10 in the oil-coal co-refining hydrogenation reaction process, and a front-positioned online hydrogenation stabilization method is formed; the method is characterized in that a temperature and high pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing a short-flow circulating solvent and a thermal and high pressure separation process R30P-HS for preparing a R30 product R30P are arranged, and the method comprises the following steps:
as shown in FIG. 4, the hot high-pressure gas R10P-HS-V enters a high-temperature high-pressure separation process R10P-HS-V-MS through a pipeline 131, and is separated into high-temperature high-pressure gas R10P-HS-V-MS-V and high-temperature high-pressure oil R10P-HS-V-MS-L, the high-temperature high-pressure oil R10P-HS-V-MS-L enters a short-flow hydrogen supply solvent oil hydrogenation stabilization reaction process R30 through a pipeline 305, and the hot high-pressure gas R30P-HS-V is used as a material flow XH.
As shown in FIG. 4, the temperature and pressure separation process R10P-HS-V-MS may use stripping hydrogen R10P-HS-V-MS-BV delivered via conduit 3151 to contact the liquid present in the temperature and pressure separation process R10P-HS-V-MS to strip the low boiling components therefrom, and the stripping gas may finally enter the temperature and pressure separation process R10P-HS-V-MS-V, as desired.
As shown in FIG. 4, the warm high-temperature oil R10P-HS-V-MS-L enters a PUMP B-PUMP through a pipeline 305 for pressurization, and then enters a short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 through a pipeline 307.
As shown in fig. 4, a precursor R30F of the short-process hydrogen supply solvent SR-DS, i.e., the pressurized high temperature and high molecular oil R10P-HS-V-MS-L, enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 through a pipe 307, and undergoes an aromatic hydrogenation partial saturation reaction in the presence of hydrogen and the short-process hydrogen supply solvent oil hydrogenation stabilization catalyst to be converted into a product R30P rich in hydrogen-supply hydrocarbons.
As shown in FIG. 4, the product R30P enters a thermal high-pressure separation process through a pipeline 311, R30P-HS is separated into thermal high-pressure gas R30P-HS-V and thermal high-pressure oil R30P-HS-L, and the thermal high-pressure oil R30P-HS-L is used as a material flow SR-DS.
As shown in FIG. 4, any suitable operating conditions may be used for the thermal high pressure separation process R30P-HS for the purpose of obtaining hydrogen donating hydrocarbons and separating out gases consisting of other components. Usually the hot high-oil R30P-HS-L is mainly composed of hydrocarbons with conventional boiling point higher than 280 ℃ or higher than 230 ℃, the operating temperature of the gas-liquid separation process is: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
As shown in FIG. 4, the high-temperature high-pressure gas R10P-HS-V-MS-V enters a post-treatment system R10P-HS-V-AUNIT through a pipeline 301.
As shown in FIG. 4, hot high-pressure separation gas R30P-HS-V is conveyed by a pipeline 341 and can enter a required position of an oil-coal co-refining hydrogenation reaction process R10.
With respect to the solution shown in FIG. 4, it is advantageous to avoid the impurity gases such as H from the hot high-split gas R10P-HS-V2O、NH3、CO、CO2And HCl enters R30, hydrogen can be reused, the process is simple, the secondary use of the hydrogen can be that multiple process points and multiple positions are used as new hydrogen, quenching hydrogen, flushing hydrogen, stripping hydrogen and the like, the use of short-process hydrogen supply solvent oil can be that multiple process points and multiple positions are used as hydrogen supply agents, flushing oil, cooling oil and the like, and the flexibility is higher.
FIG. 5 is a schematic diagram of the principle flow of the 4 th technical scheme of preparing a short-process hydrogen-donating hydrocarbon part R30-UNIT from hydrocarbon oil in hot high-pressure gas R10P-HS-V in the oil-coal co-refining method of the short-cycle hydrogen-donating solvent oil of the invention, compared with the scheme shown in FIG. 4, the method cancels the thermal high-pressure separation process R30P-HS of the R30 product R30P, and all components of hydrogen-donating hydrocarbon, hydrogen and the like in the R30 product R30P enter the required positions of the oil-coal co-refining hydrogenation process R10, such as an initial reaction space, an intermediate reaction space and a final reaction space.
In the oil-coal co-refining method using short-cycle hydrogen-supplying solvent oil, various technical schemes of circulating paths for preparing short-process hydrogen-supplying hydrocarbon preparation part R30 and/or short-cycle solvent oil from hydrocarbon oil in hot high-pressure gas R10P-HS-V are provided, and are not shown in the attached drawings, such as:
①, injecting hydrogen supply solvent SR-DS to different positions of the oil-coal co-refining hydrogenation reaction process R10 in batches and in a classified manner, introducing at least one part of short-process hydrogen supply hydrocarbon SR-DS into the middle reaction zone or the last reaction zone of the oil-coal co-refining hydrogenation reaction process R10, and introducing at least one part of high-boiling point hydrogen supply hydrocarbon into the middle reaction zone or the last reaction zone of the oil-coal co-refining hydrogenation reaction process R10;
② hydrogenation process for oil coal co-refining R10 comprises 2 or more reaction stages, wherein gas-liquid separation step is used in the interstage, at least one part of separated liquid is introduced into the next reaction zone or is hydrogenated circularly, and at least one part of separated gas is led out of the reaction system and does not enter the next reaction zone;
③ coal oil co-refining hydrogenation process R10, using quench streams such as quench hydrogen and/or quench oil;
④ high-pressure separation process R10P-HS, using gas hydrogen to reduce the content of low boiling point component in the high-temperature oil R10P-HS-L;
⑤ the high-pressure hydrogenation system of the high-boiling point hydrogen supply hydrocarbon preparation part R20 and the high-pressure hydrogenation system of the short-flow hydrogen supply hydrocarbon preparation part R30 are partially shared.
Detailed Description
The present invention is described in detail below.
The pressure in the present invention refers to absolute pressure.
The conventional boiling point of the invention refers to the vapor-liquid equilibrium temperature of a substance at one atmospheric pressure.
The conventional boiling range as referred to herein refers to the conventional boiling range of the distillate fraction.
The specific gravity of the present invention refers to the ratio of the density of a liquid at ordinary pressure and 15.6 ℃ to the density of a liquid at ordinary pressure and 15.6 ℃ unless otherwise specified.
The compositions or concentrations or amounts or yield values of the components described herein are weight basis values unless otherwise specified.
The conventional gaseous hydrocarbon refers to hydrocarbon which is gaseous under conventional conditions, and comprises methane, ethane, propane and butane.
The conventional liquid hydrocarbon refers to hydrocarbon which is liquid under conventional conditions, and includes pentane and hydrocarbon with higher boiling point.
The impurity elements in the invention refer to non-hydrogen, non-carbon and non-metal components in the raw oil, such as oxygen, sulfur, nitrogen, chlorine and the like.
The impurity component in the invention refers to the hydrogenation conversion product of non-hydrocarbon component in the raw oil, such as water, ammonia, hydrogen sulfide, hydrogen chloride and the like.
The light hydrocarbon, which is a naphtha component, referred to herein is a conventional liquid hydrocarbon having a conventional boiling point of less than 200 ℃.
The medium hydrocarbon is a diesel component, and refers to hydrocarbon with a conventional boiling point of 200-330 ℃.
The wax oil component refers to hydrocarbons with the conventional boiling point of 330-530 ℃.
The heavy hydrocarbon refers to hydrocarbon with a conventional boiling point higher than 330 ℃.
The hydrogen-oil volume ratio refers to the ratio of the standard state volume flow of hydrogen to the volume flow of a specified oil material flow at normal pressure and 20 ℃.
The aromatic ring number of the polycyclic aromatic hydrocarbon is more than or equal to 3.
In the upflow hydrogenation reactor, the macroscopic flow leading direction of the process medium in the reaction space or the hydrogenation catalyst bed layer is from top to bottom.
The present invention will be described in detail below with reference to the accompanying drawings, which are drawn for the purpose of describing the invention, but are not intended to limit the scope of the application of the invention.
The upflow expanded bed hydrogenation reactor of the invention has the following basic components:
① a reactor shell;
② openings in the reactor shell (or referred to as nipples);
③ arranged in the main upflow hydrogenation reaction space in the reactor shell, the catalyst is usually used in the working state, and the feed distribution element is usually used for evenly distributing the feed;
④ a feed distributor disposed at the bottom inside the reactor shell;
⑤ a liquid collecting cup LD and a liquid conduit LK arranged at an upper or middle section inside the reactor shell;
⑥ reactor intermediate feed distributor (or distributor), inter-catalyst bed mixers, such as cold hydrogen tanks;
⑦ outlet rectification parts such as collector, anti-vortex device for liquid phase discharge, and mixed phase product outlet pipe.
⑧ measuring instruments such as thermocouple for measuring the temperature of catalyst bed, pressure gauge for measuring the pressure at specific position of reactor system, and level meter for measuring liquid level such as glass plate, float bowl, double-flange differential pressure gauge, guided wave radar, and ray level meter;
the auxiliary components of the upflow reactor are external heat insulation materials, supporting pieces (skirts or lugs), foundations, ladders, operating platforms and possible fire-fighting accessories such as a steam fire-fighting ring. According to the geological conditions, meteorological conditions and the like of a construction area, the conditions of equipment weight, height and the like are combined, the upflow reactor needs to be driven under the foundation as required to control the settling velocity of the foundation.
The oil-coal co-refining hydrogenation process R10 of the invention generally uses an upflow reactor, and the working mode can be selected as follows:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ micro-expanded bed.
In the solvent oil hydrogenation stabilization reaction processes R20 and R30, the working modes of the used reactors can be selected as follows:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
The suspended bed reactor of the invention can be in any suitable structural form, can be an empty cylinder suspended bed reactor to form piston flow or back mixing flow with internal circulation, can be an internal circulation guide cylinder to form internal circulation flow or internal external circulation flow, can be a back mixing flow type using an external circulation pipe to make liquid in an upper reaction space flow into external circulation flow of a lower reaction space former, and can be a back mixing flow type using a top product liquid collecting and guide system to form forced internal circulation flow through a circulation pressurization system.
The characteristic parts of the present invention are described below.
The invention relates to an oil-coal co-refining method using short-cycle hydrogen supply solvent oil, which is characterized by comprising the following steps:
(1) in the oil-coal slurry preparation process M10, raw oil SHVGO of non-coal derived oil and coal powder SF are prepared into oil-coal slurry R10F;
(2) in the oil-coal co-refining hydrogenation reaction process R10, under the condition that short-process circulating solvent oil SR-DS from the step (4), hydrogen and possibly used oil-coal co-refining hydrogenation catalysts exist, the oil-coal slurry R10F is converted into a coal co-refining hydrogenation product R10P;
in the oil-coal co-refining hydrogenation reaction process R10, coal liquefaction reactions including swelling, pyrolysis, hydrocracking and hydrogenation stabilization are carried out on coal powder in the oil-coal slurry R10F, light-weight reactions including thermal cracking and hydrogenation stabilization are carried out on raw oil SHVGO in the oil-coal slurry R10F, and the short-process circulating solvent oil SR-DS has at least the function of releasing active hydrogen for pyrolysis free radicals;
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the short-process cycle solvent oil hydrogenation modification reaction process R30, under the conditions of hydrogen and a short-process cycle solvent oil hydrogenation catalyst, at least part of hydrogen-donating hydrocarbon precursors R30F containing hydrocarbon components in hot high-gas R10P-HS-V undergo partial saturation reaction of aromatic hydrocarbon hydrogenation to be converted into reaction effluents R30P rich in hydrogen-donating hydrocarbon;
the high-pressure material flow containing hydrocarbon components in the reaction effluent R30P is used as short-process circulating solvent oil SR-DS and enters an oil-coal co-refining hydrogenation reaction process R10;
a high-pressure gas stream comprising hydrogen from hot high-pressure gas R10P-HS-V is used as hydrogen-rich stream XH;
(5) separating and recovering hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in the post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV is returned to the hydrogenation reaction process for recycling.
The invention discloses a 1 st flow mode of a short-flow cycle solvent oil hydrogenation modification process R30-UNIT, which comprises the following steps:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a post-positioned online hydrogenation modification method, hot high-pressure gas R10P-HS-V directly enters a reaction process R30, a hot high-pressure separation process R30P-HS and a transfer PUMP A-PUMP of a hydrogenation modification reaction process R30 of the short-process circulating solvent and a product R30P of the R30 are arranged, and the method comprises the following steps:
① in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the hot high-pressure gas R10P-HS-V enters the reaction process R30 and is converted into a product R30P rich in hydrogen supply hydrocarbon, and hydrocarbon components carried by the hot high-pressure gas R10P-HS-V are subjected to at least partial aromatic hydrogenation saturation reaction;
② is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in the hot high-pressure separation process R30P-HS, the product R30P, at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH, and at least one part of the hot high-pressure oil R30P-HS-L is pressurized by a delivery PUMP A-PUMP and then used as material flow SR-DS to enter the oil-coal co-refining hydrogenation process R10.
The invention discloses a 2 nd flow mode of a short-flow cycle solvent oil hydrogenation modification process R30-UNIT, which comprises the following steps:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the process mode is a post-positioned online hydrogenation modification method, the hot high-temperature oil R10P-HS-V-MS-L obtained by separating hot high-temperature gas R10P-HS-V in the temperature and high-pressure separation process R10P-HS-V-MS enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, the temperature and high-pressure separation process R10P-HS-V-MS, the hydrogenation modification reaction process R30 for preparing the short-process cycle solvent, the heat and high-pressure separation process R30P-HS for R30 product R30P, and the delivery PUMP A-PUMP are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V into high-temperature high-pressure gas R10P-HS-V-MS-V and high-temperature high-pressure oil R10P-HS-V-MS-L in the high-temperature high-pressure separation process R10P-HS-V-MS;
at least a portion of the hot high partial gas R30P-HS-V is used as stream XH;
② in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the high temperature and high temperature separation oil R10P-HS-V-MS-L enters the reaction process R30 and is converted into a product R30P rich in hydrogen supply hydrocarbon, and hydrocarbon components carried by the high temperature and high temperature separation gas R10P-HS-V are subjected to at least partial aromatic hydrogenation partial saturation reaction;
③ is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in the hot high-pressure separation process R30P-HS, the product R30P, at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH, and at least one part of the hot high-pressure oil R30P-HS-L is pressurized by a delivery PUMP A-PUMP and then used as material flow SR-DS to enter the oil-coal co-refining hydrogenation process R10.
In the invention, the 3 rd flow mode of the short-flow cycle solvent oil hydrogenation modification process R30-UNIT is as follows:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F pressure-increasing material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon;
④ in the thermal high pressure separation process R30P-HS, the product R30P is separated into thermal high-pressure gas R30P-HS-V and thermal high-pressure oil R30P-HS-L, at least a part of thermal high-pressure oil R30P-HS-L is used as material flow SR-DS to enter into the oil-coal co-refining hydrogenation process R10.
The invention discloses a 4 th flow mode of a short-flow cycle solvent oil hydrogenation modification process R30-UNIT, which comprises the following steps:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F of the pressurized material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon, at least a part of hot high-fraction oil R30P-HS-L is used as the material flow SR-DS to enter the oil-coal co-refining hydrogenation reaction process R10.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the thermal high-pressure separation process R30P-HS, stripping hydrogen R30P-HS-BV can be used to contact liquid existing in the thermal high-pressure separation process R30P-HS so as to strip low boiling point components in the liquid, and stripping gas enters the thermal high-pressure gas R30P-HS-V.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, in the thermal high-pressure separation process R30P-HS, the thermal high-pressure separation oil R30P-HS-L is mainly composed of hydrocarbons with a conventional boiling point higher than 280 ℃ or higher than 230 ℃.
The invention (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and the thermal high-pressure separation process R30P-HS operating temperature: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the temperature and pressure separation process R10P-HS-V-MS, the stripping hydrogen R10P-HS-V-MS-BV can be used to contact the liquid existing in the temperature and pressure separation process R10P-HS-V-MS so as to strip the low boiling point components in the liquid, and the stripping gas can finally enter the temperature and pressure separation gas R10P-HS-V-MS-V.
According to the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, in the temperature and high pressure separation process R10P-HS-V-MS, the temperature and high-pressure separation oil R10P-HS-V-MS-L mainly comprises hydrocarbons with the conventional boiling point higher than 250 ℃ or higher than 200 ℃.
The invention (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the temperature and pressure separation process R10P-HS-V-MS operating temperature: usually 150 to 330 ℃, usually 180 to 280 ℃, preferably 200 to 250 ℃.
The invention relates to a method for preparing coal oil slurry, which comprises the following steps of (1) in the coal oil slurry preparation process M10, coal slurry R10F, mass concentration of coal powder: typically greater than 30%, typically greater than 40%, and most preferably greater than 45%.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, a pre-hydrogenation reaction section R10-DD can be arranged;
in the pre-hydrogenation reaction section R10-DD, the oil coal slurry R10F is subjected to pre-hydrogenation reaction and is converted into a coal pre-hydrogenation product R10-DD-P, and the short-process hydrogen supply solvent SR-DS plays a role in providing active hydrogen and generally plays a main role in providing the active hydrogen; generally, the ratio of the standard state volume of the hydrogen to the volume of the oil coal slurry in the pre-hydrogenation reaction section R10-DD is lower than 300: 1, so that the gasification rate of the short-flow hydrogen supply solvent SR-DS is reduced.
In the invention, (2) at least 1 intermediate product gas-liquid separation step R10-MS and at least 2 liquid stream material coal hydrogenation oil-making reaction areas which are operated in series can be arranged in the oil-coal co-refining hydrogenation reaction process R10;
at least one part of the liquid-phase-containing material discharged from the gas-liquid separation step R10-MS enters a downstream liquid stream material coal hydrogenation oil-making reaction zone;
at least a part of the gas-phase-containing material discharged from the gas-liquid separation step R10-MS does not enter a downstream liquid stream material coal hydrogenation oil-making reaction zone.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, based on the liquid stream material coal hydrogenation oil-making reaction process, hydrogen-supplying solvent can be injected in batches, namely at least 2 hydrogen-supplying hydrocarbon stream adding points are used, the first hydrogen-supplying hydrocarbon stream adding point is the initial reaction zone of the oil-coal co-refining hydrogenation reaction process R10, and the second hydrogen-supplying hydrocarbon stream adding point is positioned at the downstream of the first hydrogen-supplying hydrocarbon stream adding point.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, based on the liquid stream material coal hydrogenation oil-making reaction process, hydrogen-supplying solvents can be injected in a classified mode, namely at least 2 hydrogen-supplying hydrocarbon stream adding points are used, and a second hydrogen-supplying hydrocarbon stream adding point mainly composed of normal hydrocarbons with higher boiling points is positioned at the downstream of a first hydrogen-supplying hydrocarbon stream adding point mainly composed of normal hydrocarbons with lower boiling points.
In the invention, (3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
in the hot high pressure separation process R10P-HS, stripping hydrogen R10P-HS-BV can be used to contact liquid existing in the hot high pressure separation process R10P-HS to strip low boiling components therein; generally, the stripping gas finally enters into the hot high-pressure gas R10P-HS-V.
In the invention, (3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
typically, the hot high-molecular gas R10P-HS-V, wherein the hydrocarbons consist essentially of hydrocarbons with a conventional boiling point below 450 ℃;
generally, the hot high-molecular gas R10P-HS-V, wherein the hydrocarbon mainly comprises hydrocarbon with a conventional boiling point lower than 400 ℃;
it is possible to use hot high-molecular gases R10P-HS-V, in which the hydrocarbons consist essentially of hydrocarbons with a conventional boiling point below 350 ℃.
In the invention, (5) separating and recovering hot hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in a post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV returns to the hydrogenation reaction process for recycling, and the hydrogen volume concentration of the hydrogen-rich gas XHV is: generally greater than 70%, generally greater than 80%, preferably greater than 90%; usually, at least a part of the hydrogen-rich gas XHV is returned to the hydrogenation reaction process after purifying the hydrogen for recycling.
According to the invention, (6) in a separation/fractionation part R10P-HS-L-DS, separating hot high-grade oil R10P-HS-L to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃ or above 530 ℃;
and (3) according to the requirement, taking a part of the liquefaction residue VS as a recycle raffinate VSR to enter the oil-coal co-refining hydrogenation reaction process R10.
According to the invention, (6) in a separation/fractionation part R10P-HS-L-DS, separating hot high-grade oil R10P-HS-L to obtain liquefied product distillate oil and liquefied residue VS;
part of the liquefaction residue VS is used as a product VSP, and part of the liquefaction residue is used as a liquefaction residue circulating material VSR to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10, for example, the liquefaction residue circulating material VSR is used as a coal slurry preparation solvent oil to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through an oil-coal slurry preparation process M10.
In the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursor processed can be 1-path or 2-path or multi-path material.
In the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursor processed can be 2-path or multi-path material, and a synchronous hydrogenation mode of mixed raw material hydrocarbon is adopted.
In the invention, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursors processed can be 2 hydrogen-donating hydrocarbon precursors, the boiling ranges and the molecular structures of the 2 hydrogen-donating hydrocarbon precursors have larger difference, and the 2 hydrocarbon streams adopt asynchronous hydrogenation modes selected from 1 or more of the following methods:
① the first hydrogen donor hydrocarbon precursor is hydrogenated after being mixed with the second hydrogen donor hydrocarbon precursor;
② the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel to obtain a product, mixed and separated;
③ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel, and the obtained products are mixed and then hydrogenated again;
④ the first hydrogen-supplying hydrocarbon precursor and the second hydrogen-supplying hydrocarbon precursor are hydrogenated respectively, the products are separated under high pressure, at least one part of each high-pressure oil enters into the oil coal co-refining hydrogenation process R10.
The invention may comprise the steps of:
(6) separating hot high-fraction oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil with a conventional boiling point of 250-530 ℃ and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
(7) in the process of the solvent oil hydrogenation reaction R20, under the condition of hydrogen and a solvent oil hydrogenation catalyst, at least part of the aromatic hydrocarbon hydrogenation partial saturation reaction of the hydrogen-donating hydrocarbon precursor R20F is carried out to be converted into reaction effluent R20P rich in hydrogen-donating hydrocarbon;
a hydrogen-donating hydrocarbon precursor R20F comprising at least a portion of distillate oil ML;
in the solvent oil hydrogenation reaction process R20, the hydrogen donor hydrocarbon precursor is processed into 1-way or 2-way or multi-way material.
(8) Separating the reaction effluent R20P to obtain a long-process circulating hydrogen donor solvent LR-DS;
at least a part of the hydrogen donor solvent LR-DS enters the oil-coal co-refining hydrogenation reaction process R10.
In the invention, (7) in the solvent oil hydrogenation reaction process R20, the processed hydrogen-donating hydrocarbon precursor is 2-way or multi-way material, and a synchronous hydrogenation mode of mixed raw material hydrocarbon can be adopted.
In the invention, (7) in the solvent oil hydrogenation reaction process R20, the processed hydrogen-donating hydrocarbon precursors are 2 hydrogen-donating hydrocarbon precursors, and the boiling ranges and molecular structures of the 2 hydrogen-donating hydrocarbon precursors have large differences, and the asynchronous hydrogenation mode adopted by the 2 hydrocarbon streams can be selected from 1 or more of the following methods:
① the first hydrogen donor hydrocarbon precursor is hydrogenated after being mixed with the second hydrogen donor hydrocarbon precursor;
② the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel to obtain a product, mixed and separated;
③ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel, and the obtained products are mixed and then hydrogenated again;
④ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are hydrogenated respectively to obtain products, which are separated under high pressure, at least part of each high-pressure oil is mixed and then enters the separation/fractionation part LR-DSF.
In the invention, (2) the operation mode of the reactor used in the oil-coal co-refining hydrogenation reaction process R10 can be selected from 1 or a combination of several of the following:
① suspension bed is slurry bed;
② bubbling bed;
③ micro-expanded bed.
In the invention, (4) the hydrogenation reactor used in the short-process cycle solvent oil hydrogenation modification process R30-UNIT can be operated in a mode selected from 1 or a combination of several of the following modes:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
In the present invention, (7) the reactor used in the solvent oil hydrogenation reaction process R20 may be operated in a manner selected from 1 or a combination of several of the following:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
In general, the invention (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point of the hydrocarbons with the boiling point higher than 250 ℃ in the short-process cycle solvent oil SR-DS: the weight content of the partially saturated aromatic hydrocarbon is more than 15%, and the aromatic carbon rate is 0.35-0.70;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 15 percent, and the aromatic carbon rate is 0.35-0.70.
The invention, generally, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point of the hydrocarbons with the temperature higher than 250 ℃ in the short-process cycle solvent oil SR-DS: the weight content of the partially saturated aromatic hydrocarbon is more than 20 percent, and the aromatic carbon rate is 0.40-0.65;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 20 percent, and the aromatic carbon rate is 0.40-0.65.
The invention, preferably, (4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point of the short-process cycle solvent oil SR-DS is higher than 250 ℃ hydrocarbon: the weight content of the partially saturated aromatic hydrocarbon is more than 25%, and the aromatic carbon rate is 0.45-0.60;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 25 percent, and the aromatic carbon rate is 0.45-0.60.
In the invention, the operation conditions of the solvent oil hydrogenation reaction process are generally as follows:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W series hydrogenation catalyst; the reaction temperature is 300-390 ℃, the hydrogenation pressure is 10-25 MPa, and the gas-liquid volume ratio is 300-1000 NL/kg;
(7) in the solvent oil hydrogenation reaction process R20, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W hydrogenation catalyst; the reaction temperature is 300-390 ℃, the hydrogenation pressure is 10-25 MPa, and the gas-liquid volume ratio is 300-1000 NL/kg.
In the invention, the operation conditions of R10 in the oil-coal co-refining hydrogenation reaction process are as follows:
(2) in the oil-coal co-refining hydrogenation reaction process R10, the reaction temperature is 400-465 ℃, the reactor pressure is 6-30 MPa, the gas-liquid volume ratio is 600-1500 NL/kg, the addition amount of the liquefaction catalyst is 0.5-3 mass% of the weight of the dry coal powder, the addition amount of the cocatalyst is 1.0-2.0 of the molar ratio of S in the cocatalyst to the active metal of the catalyst, and the solid concentration of coal slurry is 45-50 mass%.
In the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, the hydrogenation catalyst which can be used is a composite hydrogenation catalyst and comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the catalyst R10C is less than 2 wt%; R10C is a powdery particle having a particle diameter of 1 to 100 μm.
According to the invention, (2) in the oil-coal co-refining hydrogenation reaction process R10, the coal hydrogenation direct liquefaction catalyst can be a nano ultrafine particle hydrated iron oxide catalyst and/or iron oxide and/or pyrite and/or hematite and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
The invention, generally, (2) in the oil coal co-refining hydrogenation reaction process R10, using fresh hydrogen and/or recycle hydrogen;
(4) in the short-flow cycle solvent oil hydrogenation modification reaction process R30, using new hydrogen and/or cycle hydrogen;
(7) fresh hydrogen and/or recycle hydrogen is used in the solvent oil hydrogenation process R20.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 1 st flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 2 nd flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through the oil-coal slurry preparation process M10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 3 rd flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 in the oil-coal slurry preparation process M10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 4 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydrogenation modification process CR10UNIT, and the CSH returns to an oil-coal co-refining hydrogenation reaction process R10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 5 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydro-upgrading process, and the CSH is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through an oil-coal slurry preparation process M10.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residue VS, and the 6 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the deasphalted distilled oil CFD obtained by the separation step of the pyrolysis tar CF, the high-pressure system of the hydrogenation modification process CR10UNIT of the CFD and the high-pressure system of the hydrogenation stabilization reaction process R20 of the solvent oil are partially or completely shared.
The invention can set a fluidized pyrolysis process BR10UNIT of liquefaction residues VS, and the 7 th flow scheme is as follows:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the deasphalted distilled oil CFD obtained by the separation step of the pyrolysis tar CF, a high-pressure system of a hydrogenation upgrading process CR10UNIT of the CFD and a high-pressure system of a hydrogenation stable reaction process R30 of the short-flow hydrogen supply solvent oil are partially or completely shared.
In the invention, (1) in the process of preparing the oil-coal slurry, M10, raw oil SHVGO is non-coal derived oil and mainly consists of hydrocarbon with the conventional boiling point higher than 530 ℃.
The general control principle of the gas phase hydrogen sulfide concentration in the hydrogenation reaction process of the present invention is described in detail below.
Any make-up sulfur may be added to any of the hydrogenation processes as desired, but is typically added to the uppermost upstream hydrogenation process inlet to ensure that the minimum hydrogen sulfide concentration necessary for the reaction process, such as 500ppm (v) or 1000ppm (v), or a desired specified value, to ensure that the hydrogen sulfide partial pressure necessary for the catalyst does not fall below the minimum specified value. The supplementary sulfur may be hydrogen sulfide or a material which can be converted into hydrogen sulfide and has no adverse effect on the hydroconversion process, such as hydrogen sulfide-containing gas or oil, or liquid sulfur or carbon disulfide or dimethyl disulfide which generates hydrogen sulfide after being contacted with high-temperature hydrogen gas.
The general principles of the high pressure separation process of the hydrogenation reaction effluent of the present invention are described in detail below.
The high-pressure separation process of the hydrogenation reaction effluent usually comprises a cold high-pressure separator, when the density of the hydrocarbon oil in the hydrogenation reaction effluent is high (for example, the density is close to the water density) or the viscosity is high or the hydrocarbon oil is difficult to separate by emulsification with water, a hot high-pressure separator with the operation temperature usually being 150-450 ℃ needs to be arranged, at the moment, the hydrogenation reaction effluent enters the hot high-pressure separator to be separated into hot high-pressure gas mainly comprising hydrogen in volume and hot high-pressure oil liquid mainly comprising conventional liquid hydrocarbon and possibly existing solids, the hot high-pressure gas enters the cold high-pressure separator with the operation temperature usually being 20-80 ℃ to be separated into cold high-pressure oil and cold high-pressure gas, and the following aims are achieved because a large amount of high-boiling-point components enter the hot high-pressure oil liquid: the cold high-fraction oil becomes less dense or less viscous or easily separated from water. The high-pressure separation process of the hydrogenation reaction effluent is provided with the hot high-pressure separator, and the high-pressure separation process also has the advantage of reducing heat loss because the hot high-pressure separation oil liquid can avoid the cooling process of using an air cooler or a water cooler for hot high-pressure separation gas. Meanwhile, part of the hot high-oil-content liquid can be returned to the upstream hydrogenation reaction process for recycling, so as to improve the overall raw material property of the hydrogenation reaction process receiving the circulating oil, or the circulating oil is subjected to circulating hydrogenation.
Before the hydrogenation reaction effluent or hot high-pressure gas enters the cold high-pressure separation part, the temperature is usually reduced (generally, heat exchange with the reaction part feed) to about 220-100 ℃ (the temperature should be higher than the crystallization temperature of the ammonium hydrosulfide in the gas phase of the hydrogenation reaction effluent), then washing water is usually injected into the reaction effluent to form a hydrogenation reaction effluent after water injection, the washing water is used for absorbing ammonia and other impurities such as hydrogen chloride and the like which may be generated, and the water solution after absorbing the ammonia necessarily absorbs the hydrogen sulfide. In the cold high-pressure separation part, the effluent of the hydrogenation reaction after water injection is separated into: a cold high-molecular gas mainly composed of hydrogen in volume, a cold high-molecular oil mainly composed of conventional liquid hydrocarbon and dissolved hydrogen, and a cold high-molecular water mainly composed of water and dissolved with ammonia and hydrogen sulfide. The cold high-moisture water generally contains 0.5-15% (w), preferably 1-8% (w) of ammonia. One purpose of the washing water injection is to absorb ammonia and hydrogen sulfide in the hydrogenation reaction effluent, prevent the formation of ammonia hydrosulfide or ammonia polysulfide crystals from blocking the heat exchanger channels, and increase the pressure drop of the system. The injection amount of the washing water is determined according to the following principle: on the one hand, the washing water is divided into vapor phase water and liquid phase water after being injected into the hydrogenation reaction effluent, and the liquid phase water amount is required to be more than zero, and is preferably 30 percent or more of the total amount of the washing water; in yet another aspect, the wash water is used to absorb ammonia from the hydrogenation effluent, to prevent the high partial gas from having too high an ammonia concentration, and to reduce the activity of the catalyst, and generally the lower the ammonia volume concentration of the high partial gas, the better, the lower the ammonia volume concentration of the high partial gas, the more preferably not greater than 200ppm (v), and most preferably not greater than 50ppm (v). The operating pressure of the cold high-pressure separator is the difference between the pressure of the hydrogenation reaction part and the actual pressure drop, and the difference between the operating pressure of the cold high-pressure separator and the hydrogenation reaction pressure is not too low or too high, generally 0.35-3.2 MPa, and generally 0.5-1.5 MPa. The hydrogen volume concentration value of the cold high-molecular gas should not be too low (leading to a rise in the operating pressure of the plant), and should generally be not less than 70% (v), preferably not less than 80% (v), and most preferably not less than 85% (v). At least one part of the cold high-molecular gas, which is usually 85-100%, is returned to the hydrogenation part for recycling so as to provide the hydrogen amount and the hydrogen concentration necessary for the hydrogenation part; in order to increase the investment efficiency of the plant, it is necessary to ensure that the recycle hydrogen concentration does not fall below the aforementioned lower limit, for which reason, depending on the specific feedstock properties, reaction conditions, product distribution, a portion of the cold high-molecular gas may be removed to remove methane and ethane produced by the reaction. For discharged cold high-molecular gas, conventional membrane separation process or pressure swing adsorption process or oil washing process can be adopted to realize the separation of hydrogen and non-hydrogen gas components, and the recovered hydrogen is used as new hydrogen.
Fresh hydrogen is fed into the hydrogenation section to replenish hydrogen consumed during the hydrogenation reaction, and the higher the concentration of fresh hydrogen, the better, the more preferably the concentration of fresh hydrogen is not lower than 95% (v), and the more preferably not lower than 99% (v). All of the fresh hydrogen may be introduced into any of the hydrogenation sections, preferably the first hydrogenation reactor.
Examples
Example one
The invention discloses an oil-coal co-refining hydrogenation process of 100 tons/hour raw material coal powder and 100 tons/hour petroleum residue, which adopts a combined method of a preposed solvent oil hydrogenation stable reaction process R30 and an oil-coal co-refining hydrogenation reaction process R10, and has the following operation conditions:
(1) in the coal oil slurry preparation process M10, coal powder SF and 100 tons/hour petroleum residue SHVGO are prepared into coal oil slurry R10F according to the weight ratio of 1: 1, and the solid concentration of the coal slurry is 50 mass percent;
(2) in the oil-coal co-refining hydrogenation reaction process R10, the reaction temperature is 400-455 ℃, the reaction pressure is 18-20 MPa, the gas-liquid volume ratio is 700-800 NL/kg, the addition amount of the liquefaction catalyst is 1.5-2 mass% of the weight of the dry coal powder, the volume concentration of gas-phase hydrogen sulfide in a reaction space is ensured to be more than 0.15%, and the retention time is 120-150 minutes (to the total volume of the raw material coal powder and the petroleum residual oil);
in the oil-coal co-refining hydrogenation reaction process R10, the used hydrogenation catalyst is a composite hydrogenation catalyst and comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is a nano ultrafine particle hydrated iron oxide catalyst;
the oil-coal co-refining hydrogenation reaction process R10 comprises 3 reaction stages, wherein a gas-liquid separation step is used in the interstage stage, the separated liquid is introduced into the next-stage reaction zone or is subjected to circulating hydrogenation, and the separated gas is led out of the reaction system and does not enter the next-stage reaction zone; each effect requires the addition of a new low impurity hydrogen feed such as fresh hydrogen and/or recycle hydrogen;
1. 2, 3, the reaction grade temperature is 400-420 ℃, 420-435 ℃ and 440-455 ℃;
1. the residence time proportion of the reaction stages 2 and 3 is 30 percent, 40 percent and 30 percent;
(3) in the thermal high-pressure separation process R10P-HS, the operation temperature is 410 ℃, and the pressure is 18-20 MPa; the oil-coal co-refining hydrogenation product R10P is separated into hot high-molecular gas R10P-HS-V and hot high-molecular oil R10P-HS-L;
in the thermal high-pressure separation process R10P-HS, gas stripping hydrogen R10P-HS-BV is used to contact liquid existing in the thermal high-pressure separation process R10P-HS so as to strip low boiling point components in the liquid, and the gas stripping gas finally enters thermal high-pressure separation gas R10P-HS-V;
hot high-molecular gas R10P-HS-V, wherein the hydrocarbon mainly comprises hydrocarbon with conventional boiling point lower than 400 ℃;
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
the operating temperature of the R10P-HS-V-MS in the temperature and pressure separation process is 180-280 ℃;
the high-temperature oil R10P-HS-V-MS-L mainly comprises hydrocarbons with the conventional boiling point of 250-400 ℃;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F pressure-increasing material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon;
in the solvent oil hydrogenation stabilization reaction process R30, the conventional boiling point of the reaction effluent R30P is higher than that of the hydrocarbons at 250 ℃: the weight content of the partially saturated aromatic hydrocarbon is more than 20%, and the aromatic carbon rate is 0.45-0.60; in the solvent oil hydrogenation stable reaction process R30, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W hydrogenation catalyst; the reaction temperature is 340-360 ℃, the hydrogenation pressure is 18-20 MPa, and the gas-liquid volume ratio is 600-800 NL/kg;
④ is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in a hot high-pressure separation process R30P-HS, a product R30P, at least one part of the hot high-pressure oil R30P-HS-L is used as material flow SR-DS, and the hot high-pressure gas can be flexibly injected into an initial reaction space, a middle reaction space and a tail end reaction space of R10 at different positions of an oil-coal co-refining hydrogenation reaction process R10 by multi-point injection;
the operating temperature of the R30P-HS in the hot high-pressure separation process is 180-280 ℃;
the hot high-molecular oil R30P-HS-L mainly comprises hydrocarbons with the conventional boiling point higher than 250 ℃;
the weight flow of the short-process circulating hydrogen supply solvent SR-DS and the weight flow of the raw oil SF are controlled according to the ratio of 2: 1;
(5) separating and recovering hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in the post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV returns to the hydrogenation reaction process (the solvent oil hydrogenation stabilization reaction process) for recycling after passing through the hydrogen purification process, and the volume concentration of the hydrogen returning to the hydrogenation reaction process is more than 90 percent;
(6) separating the hot high-fraction oil R10P-HS-L in a separation/fractionation section R10P-HS-L-DS to obtain a liquefied product fraction ML and a liquefied residue VS mainly composed of hydrocarbons having a conventional boiling point higher than 520 ℃.
Example two
Based on the first embodiment, the following steps are added:
(7) in the solvent oil hydrogenation stable reaction process R20, under the condition of hydrogen and solvent oil hydrogenation catalyst, at least part of aromatic hydrocarbon hydrogenation partial saturation reaction of hydrogen-supplying hydrocarbon precursor R20F is converted into reaction effluent R20P rich in hydrogen-supplying hydrocarbon;
in the solvent oil hydrogenation stabilization reaction process R20, the conventional boiling point of the reaction effluent R20P is higher than that of the hydrocarbons at 250 ℃: the weight content of the partially saturated aromatic hydrocarbon is more than 20%, and the aromatic carbon rate is 0.45-0.60; in the solvent oil hydrogenation stable reaction process R20, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W hydrogenation catalyst; the reaction temperature is 350-370 ℃, the hydrogenation pressure is 18-20 MPa, and the gas-liquid volume ratio is 500-600 NL/kg;
a hydrogen-donating hydrocarbon precursor R20F comprising at least a portion of distillate oil ML consisting essentially of hydrocarbons having a conventional boiling point of from 330 ℃ to 530 ℃;
(8) in the thermal high-pressure separation process R20P-HS, the operation temperature is 230 ℃, and the pressure is 18-20 MPa; the solvent oil hydrogenation reaction product R20P is separated into hot high-molecular gas R20P-HS-V and hot high-molecular oil R20P-HS-L;
hot high-molecular gas R20P-V, wherein the hydrocarbon mainly comprises hydrocarbon with conventional boiling point lower than 250 ℃;
(9) separating hot high-fraction oil R20P-HS-L from a separation/fractionation part LR-DSF to obtain a long-flow circulating hydrogen donor solvent LR-DS;
the weight flow of the hydrogen donor solvent LR-DS and the weight flow of the raw oil SF are controlled according to the ratio of 0.5: 1;
30 percent of hydrogen-supplying solvent LR-DS enters a second-stage reaction zone of the oil-coal co-refining hydrogenation reaction process R10, and 70 percent of hydrogen-supplying solvent LR-DS enters a third-stage reaction zone of the oil-coal co-refining hydrogenation reaction process R10.
EXAMPLE III
Based on the first embodiment, the following steps are added:
80% of the liquefaction residue VS is used as a product residual liquid VSP, 20% of the liquefaction residue VS is used as a liquefaction residue circulating material VSR, and the liquefaction residue VSR is used as a coal slurry preparation solvent to circularly return to the oil-coal co-refining hydrogenation reaction process R10 in the coal-oil slurry preparation process M10.
Example four
Based on the first embodiment, the following steps are added:
and (3) taking the liquefied residue VS as a product residual VSP, entering a fluidized pyrolysis process BR10UNIT, and converting into coal gas, pyrolysis tar CF and pyrolysis semicoke.
EXAMPLE five
Based on the fourth embodiment, the following steps are added:
the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through the oil-coal slurry preparation process M10.
EXAMPLE six
Based on the fourth embodiment, the following steps are added:
deasphalting distilled oil CFD obtained by the separation step of the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 in the oil-coal slurry preparation process M10.
EXAMPLE seven
Based on the sixth embodiment, the following steps are added:
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydrogenation modification process CR10UNIT, and the CSH returns to an oil-coal co-refining hydrogenation reaction process R10.
Example eight
Based on the sixth embodiment, the following steps are added:
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydro-upgrading process, and the CSH is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through an oil-coal slurry preparation process M10.
Example nine
Based on the seventh embodiment, the deasphalted distillate oil CFD obtained from the separation step of the pyrolysis tar CF, the high pressure system of the hydrogenation upgrading process CR10UNIT of CFD, and the high pressure system of the hydrogenation stabilization reaction process R20 of the solvent oil are partially or completely shared.
Example ten
Based on the seventh embodiment, the deasphalted distillate oil CFD obtained from the separation step of the pyrolysis tar CF, the high pressure system of the hydrogenation upgrading process CR10UNIT of the CFD, and the high pressure system of the hydrogenation stabilization reaction process R30 of the short-flow hydrogen-supplying solvent oil are partially or completely shared.
Claims (64)
1. A method for jointly refining oil and coal by using short-cycle hydrogen supply solvent oil is characterized by comprising the following steps:
(1) in the oil-coal slurry preparation process M10, raw oil SHVGO of non-coal derived oil and coal powder SF are prepared into oil-coal slurry R10F;
(2) in the oil-coal co-refining hydrogenation reaction process R10, under the condition that short-process circulating solvent oil SR-DS from the step (4), hydrogen and possibly used oil-coal co-refining hydrogenation catalysts exist, the oil-coal slurry R10F is converted into a coal co-refining hydrogenation product R10P;
in the oil-coal co-refining hydrogenation reaction process R10, coal liquefaction reactions including swelling, pyrolysis, hydrocracking and hydrogenation stabilization are carried out on coal powder in the oil-coal slurry R10F, light-weight reactions including thermal cracking and hydrogenation stabilization are carried out on raw oil SHVGO in the oil-coal slurry R10F, and the short-process circulating solvent oil SR-DS has at least the function of releasing active hydrogen for pyrolysis free radicals;
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT and in the short-process cycle solvent oil hydrogenation modification reaction process R30, under the conditions of hydrogen and a short-process cycle solvent oil hydrogenation catalyst, at least part of hydrogen-donating hydrocarbon precursors R30F containing hydrocarbon components in hot high-gas R10P-HS-V undergo partial saturation reaction of aromatic hydrocarbon hydrogenation to be converted into reaction effluents R30P rich in hydrogen-donating hydrocarbon;
the high-pressure material flow containing hydrocarbon components in the reaction effluent R30P is used as short-process circulating solvent oil SR-DS and enters an oil-coal co-refining hydrogenation reaction process R10;
a high-pressure gas stream comprising hydrogen from hot high-pressure gas R10P-HS-V is used as hydrogen-rich stream XH;
(5) separating and recovering hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in the post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV is returned to the hydrogenation reaction process for recycling.
2. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a post-positioned online hydrogenation modification method, hot high-pressure gas R10P-HS-V directly enters a reaction process R30, a hot high-pressure separation process R30P-HS and a transfer PUMP A-PUMP of a hydrogenation modification reaction process R30 of the short-process circulating solvent and a product R30P of the R30 are arranged, and the method comprises the following steps:
① in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the hot high-pressure gas R10P-HS-V enters the reaction process R30 and is converted into a product R30P rich in hydrogen supply hydrocarbon, and hydrocarbon components carried by the hot high-pressure gas R10P-HS-V are subjected to at least partial aromatic hydrogenation saturation reaction;
② is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in the hot high-pressure separation process R30P-HS, the product R30P, at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH, and at least one part of the hot high-pressure oil R30P-HS-L is pressurized by a delivery PUMP A-PUMP and then used as material flow SR-DS to enter the oil-coal co-refining hydrogenation process R10.
3. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the process mode is a post-positioned online hydrogenation modification method, the hot high-temperature oil R10P-HS-V-MS-L obtained by separating hot high-temperature gas R10P-HS-V in the temperature and high-pressure separation process R10P-HS-V-MS enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, the temperature and high-pressure separation process R10P-HS-V-MS, the hydrogenation modification reaction process R30 for preparing the short-process cycle solvent, the heat and high-pressure separation process R30P-HS for R30 product R30P, and the delivery PUMP A-PUMP are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V into high-temperature high-pressure gas R10P-HS-V-MS-V and high-temperature high-pressure oil R10P-HS-V-MS-L in the high-temperature high-pressure separation process R10P-HS-V-MS;
at least a portion of the hot high partial gas R30P-HS-V is used as stream XH;
② in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, in the presence of hydrogen and a short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, the high temperature and high temperature separation oil R10P-HS-V-MS-L enters the reaction process R30 and is converted into a product R30P rich in hydrogen supply hydrocarbon, and hydrocarbon components carried by the high temperature and high temperature separation gas R10P-HS-V are subjected to at least partial aromatic hydrogenation partial saturation reaction;
③ is separated into hot high-pressure gas R30P-HS-V and hot high-pressure oil R30P-HS-L in the hot high-pressure separation process R30P-HS, the product R30P, at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH, and at least one part of the hot high-pressure oil R30P-HS-L is pressurized by a delivery PUMP A-PUMP and then used as material flow SR-DS to enter the oil-coal co-refining hydrogenation process R10.
4. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F pressure-increasing material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon;
④ in the thermal high pressure separation process R30P-HS, the product R30P is separated into thermal high-pressure gas R30P-HS-V and thermal high-pressure oil R30P-HS-L, at least a part of thermal high-pressure oil R30P-HS-L is used as material flow SR-DS to enter into the oil-coal co-refining hydrogenation process R10.
5. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the process mode is a preposed online hydrogenation modification method, a temperature high-pressure separation process R10P-HS-V-MS, a delivery PUMP B-PUMP, a hydrogenation modification reaction process R30 for preparing the short-process circulating solvent, and a heat high-pressure separation process R30P-HS of a product R30P of the R30 are arranged, and the method comprises the following steps:
① separating the hot high-pressure gas R10P-HS-V-MS and the hot high-pressure gas R10P-HS-V into a hot high-pressure gas R10P-HS-V-MS-V and a hot high-pressure oil R10P-HS-V-MS-L in the temperature and high-pressure separation process, wherein at least one part of the hot high-pressure gas R30P-HS-V is used as material flow XH;
② in the pressurizing process B-PUMP, the high temperature oil R10P-HS-V-MS-L is pressurized by the PUMP B-PUMP and then enters the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30 as the pressurized material flow R10P-HS-V-MS-L-P;
③ in the short-process hydrogen supply solvent oil hydrogenation stabilization reaction process R30, as the short-process hydrogen supply solvent SR-DS precursor R30F of the pressurized material flow R10P-HS-V-MS-L-P, in the presence of hydrogen and short-process hydrogen supply solvent oil hydrogenation stabilization catalyst, at least a part of aromatic hydrogenation partial saturation reaction occurs, and the product is converted into a product R30P rich in hydrogen supply hydrocarbon, at least a part of hot high-fraction oil R30P-HS-L is used as the material flow SR-DS to enter the oil-coal co-refining hydrogenation reaction process R10.
6. The oil-coal co-refining method according to claim 2, 3 or 4, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, in the thermal high-pressure separation process R30P-HS, gas stripping hydrogen R30P-HS-BV is used to contact liquid existing in the thermal high-pressure separation process R30P-HS so as to strip low boiling point components in the liquid, and the gas stripping gas enters the thermal high-pressure gas R30P-HS-V.
7. The oil-coal co-refining method according to claim 2, 3 or 4, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, in the thermal high-pressure separation process R30P-HS, the thermal high-pressure separation oil R30P-HS-L is mainly composed of hydrocarbons with conventional boiling point higher than 280 ℃.
8. The oil-coal co-refining method according to claim 2, 3 or 4, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, in the thermal high-pressure separation process R30P-HS, the thermal high-pressure separation oil R30P-HS-L is mainly composed of hydrocarbons with conventional boiling point higher than 230 ℃.
9. The oil-coal co-refining method according to claim 2, 3 or 4, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the operation temperature of the hot high-pressure separation process R30P-HS is 150-330 ℃.
10. The oil-coal co-refining method according to claim 2, 3 or 4, characterized in that:
(4) the operation temperature of the short-flow cycle solvent oil hydrogenation modification process R30-UNIT and the thermal high-pressure separation process R30P-HS is 180-280 ℃.
11. The oil-coal co-refining method according to claim 2, 3 or 4, characterized in that:
(4) the operation temperature of the short-process circulating solvent oil hydrogenation modification process R30-UNIT and the hot high-pressure separation process R30P-HS is 200-250 ℃.
12. The oil-coal co-refining method according to claim 3, 4 or 5, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, in the temperature and pressure separation process R10P-HS-V-MS, stripping hydrogen R10P-HS-V-MS-BV is used to contact liquid existing in the temperature and pressure separation process R10P-HS-V-MS so as to strip low boiling point components in the liquid, and the stripping gas can finally enter the temperature and pressure gas R10P-HS-V-MS-V.
13. The oil-coal co-refining method according to claim 3, 4 or 5, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, in the temperature and high pressure separation process R10P-HS-V-MS, the temperature and high pressure separation oil R10P-HS-V-MS-L is mainly composed of hydrocarbons with the conventional boiling point higher than 250 ℃.
14. The oil-coal co-refining method according to claim 3, 4 or 5, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, in the temperature and high pressure separation process R10P-HS-V-MS, the temperature and high pressure separation oil R10P-HS-V-MS-L is mainly composed of hydrocarbons with conventional boiling point higher than 200 ℃.
15. The oil-coal co-refining method according to claim 3, 4 or 5, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the operation temperature of the high-temperature high-pressure separation process R10P-HS-V-MS is 150-330 ℃.
16. The oil-coal co-refining method according to claim 3, 4 or 5, characterized in that:
(4) the operation temperature of the short-process circulating solvent oil hydrogenation modification process R30-UNIT and the temperature and pressure separation process R10P-HS-V-MS is 180-280 ℃.
17. The oil-coal co-refining method according to claim 3, 4 or 5, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the operation temperature of the high-temperature high-pressure separation process R10P-HS-V-MS is 200-250 ℃.
18. The oil-coal co-refining method according to claim 1, characterized in that:
(1) in the coal oil slurry preparation process M10, the mass concentration of the coal powder in the coal slurry R10F is more than 30 percent.
19. The oil-coal co-refining method according to claim 1, characterized in that:
(1) in the coal oil slurry preparation process M10, the mass concentration of the coal powder in the coal slurry R10F is more than 40 percent.
20. The oil-coal co-refining method according to claim 1, characterized in that:
(1) in the coal oil slurry preparation process M10, the mass concentration of the coal powder in the coal slurry R10F is more than 45%.
21. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, a pre-hydrogenation reaction section R10-DD is arranged;
in the pre-hydrogenation reaction section R10-DD, the oil coal slurry R10F is subjected to pre-hydrogenation reaction and is converted into a coal pre-hydrogenation product R10-DD-P, and the short-process hydrogen supply solvent SR-DS plays a role in providing active hydrogen.
22. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, a pre-hydrogenation reaction section R10-DD is arranged;
in the pre-hydrogenation reaction section R10-DD, the coal oil slurry R10F is subjected to pre-hydrogenation reaction and is converted into a pre-hydrogenation product R10-DD-P, and the short-process circulating solvent oil SR-DS plays a main role in providing active hydrogen.
23. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, a pre-hydrogenation reaction section R10-DD is arranged;
in the pre-hydrogenation reaction section R10-DD, the oil coal slurry R10F is subjected to pre-hydrogenation reaction and is converted into a pre-hydrogenation product R10-DD-P, and the short-process circulating solvent oil SR-DS plays a main role in providing active hydrogen;
the volume ratio of the standard state volume of the hydrogen to the coal oil slurry in the pre-hydrogenation reaction section R10-DD is lower than 300: 1.
24. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, at least 1 intermediate product gas-liquid separation step R10-MS is arranged, and at least 2 liquid stream material coal hydrogenation oil-making reaction zones which are operated in series are arranged;
at least one part of the liquid-phase-containing material discharged from the gas-liquid separation step R10-MS enters a downstream liquid stream material coal hydrogenation oil-making reaction zone;
at least a part of the gas-phase-containing material discharged from the gas-liquid separation step R10-MS does not enter a downstream liquid stream material coal hydrogenation oil-making reaction zone.
25. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, based on the liquid stream material coal hydrogenation oil-making reaction process, hydrogen-supplying solvent is injected in batches, namely at least 2 hydrogen-supplying hydrocarbon stream adding points are used, the first hydrogen-supplying hydrocarbon stream adding point is the initial reaction area of the oil-coal co-refining hydrogenation reaction process R10, and the second hydrogen-supplying hydrocarbon stream adding point is positioned at the downstream of the first hydrogen-supplying hydrocarbon stream adding point.
26. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, based on the liquid stream material coal hydrogenation oil-making reaction process, hydrogen-supplying solvents are injected in classification, that is, at least 2 hydrogen-supplying hydrocarbon stream adding points are used, and a second hydrogen-supplying hydrocarbon stream adding point mainly composed of normal hydrocarbons with higher boiling points is positioned at the downstream of a first hydrogen-supplying hydrocarbon stream adding point mainly composed of normal hydrocarbons with lower boiling points.
27. The oil-coal co-refining method according to claim 1, characterized in that:
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
in the hot high pressure separation process R10P-HS, stripping hydrogen R10P-HS-BV is used to contact liquid existing in the hot high pressure separation process R10P-HS to strip low boiling components therein.
28. The oil-coal co-refining method according to claim 1, characterized in that:
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
in the hot high-pressure separation process R10P-HS, stripping hydrogen R10P-HS-BV is used to contact liquid existing in the hot high-pressure separation process R10P-HS so as to strip low boiling point components in the liquid, and the stripping gas finally enters hot high-pressure separation gas R10P-HS-V.
29. The oil-coal co-refining method according to claim 1, characterized in that:
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
hot high-molecular gas R10P-HS-V, wherein the hydrocarbon mainly comprises hydrocarbon with conventional boiling point lower than 450 ℃.
30. The oil-coal co-refining method according to claim 1, characterized in that:
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
hot high-molecular gas R10P-HS-V, wherein the hydrocarbon mainly comprises hydrocarbon with conventional boiling point lower than 400 ℃.
31. The oil-coal co-refining method according to claim 1, characterized in that:
(3) in the thermal high-pressure separation process R10P-HS, the coal co-refining hydrogenation product R10P is separated into thermal high-pressure gas R10P-HS-V and thermal high-pressure oil R10P-HS-L;
hot high-molecular gas R10P-HS-V, wherein the hydrocarbon mainly comprises hydrocarbon with conventional boiling point lower than 350 ℃.
32. The oil-coal co-refining method according to claim 1, characterized in that:
(5) separating and recovering the hot hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in a post-treatment system R10P-HS-V-AUNIT; and at least part of the hydrogen-rich gas XHV returns to the hydrogenation reaction process for recycling, and the hydrogen volume concentration of the hydrogen-rich gas XHV is more than 70 percent.
33. The oil-coal co-refining method according to claim 1, characterized in that:
(5) separating and recovering the hot hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in a post-treatment system R10P-HS-V-AUNIT; and at least part of the hydrogen-rich gas XHV returns to the hydrogenation reaction process for recycling, and the hydrogen volume concentration of the hydrogen-rich gas XHV is more than 80 percent.
34. The oil-coal co-refining method according to claim 1, characterized in that:
(5) separating and recovering the hot hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in a post-treatment system R10P-HS-V-AUNIT; and at least part of the hydrogen-rich gas XHV returns to the hydrogenation reaction process for recycling, and the hydrogen volume concentration of the hydrogen-rich gas XHV is more than 90 percent.
35. The oil-coal co-refining method according to claim 1, characterized in that:
(5) separating and recovering the hot hydrogen-rich gas XH to obtain hydrogen-rich gas XHV and hydrocarbon oil XHL in a post-treatment system R10P-HS-V-AUNIT; at least part of the hydrogen-rich gas XHV is returned to the hydrogenation reaction process for recycling after being purified.
36. The oil-coal co-refining method according to claim 1, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
and a part of the liquefaction residue VS is used as a circulating raffinate VSR to enter an oil-coal co-refining hydrogenation reaction process R10.
37. The oil-coal co-refining method according to claim 1, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 530 ℃;
and a part of the liquefaction residue VS is used as a circulating raffinate VSR to enter an oil-coal co-refining hydrogenation reaction process R10.
38. The oil-coal co-refining method according to claim 1, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS;
and part of the liquefaction residue VS is used as a product VSP, and part of the liquefaction residue is used as a liquefaction residue circulating material VSR to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10.
39. The oil-coal co-refining method according to claim 1, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS;
and (3) taking partial liquefaction residue VS as a product VSP, taking partial liquefaction residue as a liquefaction residue circulating material VSR, and taking the partial liquefaction residue as coal slurry preparation solvent oil to circulate back to the oil-coal co-refining hydrogenation reaction process R10 in the coal-oil slurry preparation process M10.
40. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, the hydrogen-donating hydrocarbon precursor is processed into 1-path or 2-path or multi-path material.
41. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the processed hydrogen-donating hydrocarbon precursor is 2-path or multi-path material, and a synchronous hydrogenation mode of mixed raw material hydrocarbon is adopted.
42. The oil-coal co-refining method according to claim 1, characterized in that:
(4) in the short-flow cycle solvent oil hydrogenation modification process R30-UNIT, the processed hydrogen-donating hydrocarbon precursors are 2 hydrogen-donating hydrocarbon precursors, the boiling range and the molecular structure of the 2 hydrogen-donating hydrocarbon precursors are greatly different, and the 2 hydrocarbon streams adopt asynchronous hydrogenation modes selected from 1 or more of the following methods:
① the first hydrogen donor hydrocarbon precursor is hydrogenated after being mixed with the second hydrogen donor hydrocarbon precursor;
② the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel to obtain a product, mixed and separated;
③ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel, and the obtained products are mixed and then hydrogenated again;
④ the first hydrogen-supplying hydrocarbon precursor and the second hydrogen-supplying hydrocarbon precursor are hydrogenated respectively, the products are separated under high pressure, at least one part of each high-pressure oil enters into the oil coal co-refining hydrogenation process R10.
43. The oil-coal co-refining method according to claim 1, characterized in that:
(6) separating hot high-fraction oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil with a conventional boiling point of 250-530 ℃ and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
(7) in the process of the solvent oil hydrogenation reaction R20, under the condition of hydrogen and a solvent oil hydrogenation catalyst, at least part of the aromatic hydrocarbon hydrogenation partial saturation reaction of the hydrogen-donating hydrocarbon precursor R20F is carried out to be converted into reaction effluent R20P rich in hydrogen-donating hydrocarbon;
a hydrogen-donating hydrocarbon precursor R20F comprising at least a portion of distillate oil ML;
in the process of the solvent oil hydrogenation reaction R20, the processed hydrogen-donating hydrocarbon precursor is a 1-path or 2-path or multi-path material;
(8) separating the reaction effluent R20P to obtain a long-process circulating hydrogen donor solvent LR-DS;
at least a part of the hydrogen donor solvent LR-DS enters the oil-coal co-refining hydrogenation reaction process R10.
44. The oil-coal co-refining method according to claim 1, characterized in that:
(7) in the process of the solvent oil hydrogenation reaction R20, the processed hydrogen-donating hydrocarbon precursor is 2-path or multi-path material, and a synchronous hydrogenation mode of mixed raw material hydrocarbon is adopted.
45. The oil-coal co-refining method according to claim 1, characterized in that:
(7) in the solvent oil hydrogenation reaction process R20, the processed hydrogen-donating hydrocarbon precursors are 2 hydrogen-donating hydrocarbon precursors, the boiling range and molecular structure of the 2 hydrogen-donating hydrocarbon precursors are greatly different, and the 2 hydrocarbon streams adopt asynchronous hydrogenation modes selected from 1 or more of the following methods:
① the first hydrogen donor hydrocarbon precursor is hydrogenated after being mixed with the second hydrogen donor hydrocarbon precursor;
② the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel to obtain a product, mixed and separated;
③ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are respectively hydrogenated in parallel, and the obtained products are mixed and then hydrogenated again;
④ the first hydrogen-donating hydrocarbon precursor and the second hydrogen-donating hydrocarbon precursor are hydrogenated respectively to obtain products, which are separated under high pressure, at least part of each high-pressure oil is mixed and then enters the separation/fractionation part LR-DSF.
46. The oil-coal co-refining method according to claim 1, characterized in that:
(2) the operation mode of the reactor used in the oil-coal co-refining hydrogenation reaction process R10 is selected from 1 or a combination of several of the following:
① suspension bed is slurry bed;
② bubbling bed;
③ micro-expanded bed.
47. The oil-coal co-refining method according to claim 1, characterized in that:
(4) the short-flow cycle solvent oil hydrogenation modification process R30-UNIT uses a hydrogenation reactor operating mode selected from 1 or a combination of several of the following:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
48. The oil-coal co-refining method according to claim 43, characterized in that:
(7) the reactor used in the solvent oil hydrogenation reaction process R20 is operated in a mode selected from 1 or a combination of several of the following modes:
① suspension bed hydrogenation reactor;
② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;
③ upflow micro-expanded bed;
④ upflow fixed bed;
⑤ downflow fixed bed;
⑥ liquid phase large circulation hydrogenation reactor with low hydrogen-oil volume ratio.
49. The oil-coal co-refining method according to claim 43, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point in the short-process cycle solvent oil SR-DS is higher than 250 ℃ hydrocarbon: the weight content of the partially saturated aromatic hydrocarbon is more than 15%, and the aromatic carbon rate is 0.35-0.70;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 15 percent, and the aromatic carbon rate is 0.35-0.70.
50. The oil-coal co-refining method according to claim 43, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point in the short-process cycle solvent oil SR-DS is higher than 250 ℃ hydrocarbon: the weight content of the partially saturated aromatic hydrocarbon is more than 20 percent, and the aromatic carbon rate is 0.40-0.65;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 20 percent, and the aromatic carbon rate is 0.40-0.65.
51. The oil-coal co-refining method according to claim 43, characterized in that:
(4) in the short-process cycle solvent oil hydrogenation modification process R30-UNIT, the normal boiling point in the short-process cycle solvent oil SR-DS is higher than 250 ℃ hydrocarbon: the weight content of the partially saturated aromatic hydrocarbon is more than 25%, and the aromatic carbon rate is 0.45-0.60;
(7) in the course of the hydrogenation of the solvent oil R20, the conventional boiling point in the reaction effluent R20P is above 250 ℃ for the hydrocarbons: the weight content of the partially saturated aromatic hydrocarbon is more than 25 percent, and the aromatic carbon rate is 0.45-0.60.
52. The oil-coal co-refining method according to claim 43, characterized in that:
(4) in the short-process circulating solvent oil hydrogenation modification process R30-UNIT, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W series hydrogenation catalyst; the reaction temperature is 300-390 ℃, the hydrogenation pressure is 10-25 MPa, and the gas-liquid volume ratio is 300-1000 NL/kg;
(7) in the solvent oil hydrogenation reaction process R20, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W hydrogenation catalyst; the reaction temperature is 300-390 ℃, the hydrogenation pressure is 10-25 MPa, and the gas-liquid volume ratio is 300-1000 NL/kg.
53. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, the reaction temperature is 400-465 ℃, the reactor pressure is 6-30 MPa, the gas-liquid volume ratio is 600-1500 NL/kg, the addition amount of the liquefaction catalyst is 0.5-3 mass% of the weight of the dry coal powder, the addition amount of the cocatalyst is 1.0-2.0 of the molar ratio of S in the cocatalyst to the active metal of the catalyst, and the solid concentration of coal slurry is 45-50 mass%.
54. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, the used hydrogenation catalyst is a composite hydrogenation catalyst and comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the catalyst R10C is less than 2 wt%; R10C is a powdery particle having a particle diameter of 1 to 100 μm.
55. The oil-coal co-refining method according to claim 1, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, the coal hydrogenation direct liquefaction catalyst is a nanometer ultrafine particle hydrated iron oxide catalyst and/or iron oxide and/or pyrite and/or hematite and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
56. The oil-coal co-refining method according to claim 43, characterized in that:
(2) in the oil-coal co-refining hydrogenation reaction process R10, using fresh hydrogen and/or recycle hydrogen;
(4) in the short-flow cycle solvent oil hydrogenation modification reaction process R30, using new hydrogen and/or cycle hydrogen;
(7) fresh hydrogen and/or recycle hydrogen is used in the solvent oil hydrogenation process R20.
57. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke.
58. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through the oil-coal slurry preparation process M10.
59. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of the pyrolysis tar CF is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 in the oil-coal slurry preparation process M10.
60. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydrogenation modification process CR10UNIT, and the CSH returns to an oil-coal co-refining hydrogenation reaction process R10.
61. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
deasphalting distilled oil CFD obtained by the separation step of pyrolysis tar CF is converted into hydrogen-donating solvent oil CSH rich in hydrogen-donating hydrocarbon through a hydro-upgrading process, and the CSH is used as a coal slurry preparation solvent to be circularly returned to the oil-coal co-refining hydrogenation reaction process R10 through an oil-coal slurry preparation process M10.
62. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the deasphalted distilled oil CFD obtained by the separation step of the pyrolysis tar CF, the high-pressure system of the hydrogenation modification process CR10UNIT of the CFD and the high-pressure system of the hydrogenation stabilization reaction process R20 of the solvent oil are partially or completely shared.
63. The oil-coal co-refining method according to claim 36, characterized in that:
(6) separating hot high-grade oil R10P-HS-L in a separation/fractionation part R10P-HS-L-DS to obtain liquefied product distillate oil and liquefied residue VS; the conventional boiling point of most of the hydrocarbons in the liquefaction residue VS is above 500 ℃;
at least one part of the liquefaction residue VS is used as a product residual VSP, enters a fluidized pyrolysis process BR10UNIT, and is converted into coal gas, pyrolysis tar CF and pyrolysis semicoke;
the deasphalted distilled oil CFD obtained by the separation step of the pyrolysis tar CF, a high-pressure system of a hydrogenation upgrading process CR10UNIT of the CFD and a high-pressure system of a hydrogenation stable reaction process R30 of the short-flow hydrogen supply solvent oil are partially or completely shared.
64. The oil-coal co-refining method according to claim 1, characterized in that:
(1) in the process M10, the raw material SHVGO is non-coal derived oil and mainly consists of hydrocarbons with conventional boiling point higher than 530 ℃.
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| CN106167717A (en) * | 2016-06-29 | 2016-11-30 | 何巨堂 | A kind of up flow type heat from hydrogenation cracking method of high aromatic carbon rate poor quality hydrocarbon branch charging |
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| CN106167717A (en) * | 2016-06-29 | 2016-11-30 | 何巨堂 | A kind of up flow type heat from hydrogenation cracking method of high aromatic carbon rate poor quality hydrocarbon branch charging |
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