CN109054893B - System for hydrogen purification and wax oil hydrogenation coupling in coal hydrogen production - Google Patents
System for hydrogen purification and wax oil hydrogenation coupling in coal hydrogen production Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 127
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 127
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000746 purification Methods 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 239000003245 coal Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 230000008878 coupling Effects 0.000 title claims abstract description 11
- 238000010168 coupling process Methods 0.000 title claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 53
- 238000000926 separation method Methods 0.000 claims abstract description 48
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 15
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000009615 deamination Effects 0.000 claims description 5
- 238000006481 deamination reaction Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- -1 heterocyclic nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and provides a system for hydrogen purification and wax oil hydrogenation coupling in coal hydrogen production. Firstly, separating carbon dioxide in the converted gas from the coal hydrogen production by using a two-stage carbon membrane separator, then mixing the residual gas of the first-stage carbon membrane with the circulating hydrogen from the hydrogenation unit, then feeding the mixture into a hydrogen membrane separator, removing a small amount of carbon dioxide and hydrogen sulfide in the product hydrogen, feeding the product hydrogen into a wax oil hydrogenation refining unit for hydrogenation, finally carrying out oil-gas separation, and feeding the circulating hydrogen into the front of the hydrogen membrane separator. The invention can realize high coupling of hydrogen purification and utilization, not only reduces the investment and the operating cost of a hydrogen purification unit, but also reduces the partial pressure of hydrogenation and improves the hydrogenation efficiency of wax oil.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a system for hydrogen purification and wax oil hydrogenation coupling in coal-to-hydrogen.
Background
The Fluid Catalytic Cracking (FCC) process is one of the most effective technologies for converting heavy oil into high-value products such as gasoline, diesel oil, liquefied gas and the like, and is widely applied to the world oil refining industry due to strong raw material adaptability, high product added value and good economic benefit, so that the FCC process is the most important secondary processing means of petroleum.
The wax oil hydrotreating technology was applied in the 70's of the 20 th century, and the initial purpose was to produce low sulfur fuel oil and reduce the sulfide emissions from the regenerator of the FCC unit, meeting the environmental regulations. In recent years, it has been recognized that nitrogen and aromatics in the FCC feed are key factors affecting the efficiency of an FCC unit, and reducing the feed nitrogen and aromatics content can increase the unit gasoline yield and increase the efficiency. Therefore, the method for improving the denitrification rate while desulfurizing the crude oil by the crude oil hydrotreating process and realizing aromatic hydrocarbon saturation is a main way for improving the profit of an FCC device and is also a new requirement for the FCC raw material hydrotreating process.
Along with the quality of crude oil in the world becoming worse and the environmental protection regulations becoming stricter, the crude oil hydrogenation process will be further and rapidly developed, and the hydrogen consumption will be gradually increased. Among them, an important source of hydrogen for crude oil hydrogenation is Integrated Gasification Combined Cycle (IGCC) power generation systems.
IGCC is a technology of changing coal into hydrogen by burning coal, the coal is converted into synthesis gas containing carbon monoxide and hydrogen by gasification and purification treatment such as desulfurization and dust removal, and the synthesis gas is then fed into a gas turbine to generate electricity. IGCC has great potential not only in the aspects of less emission of sulfur dioxide, nitrogen oxides and dust, but also in the aspect of controlling the emission of greenhouse gases.
The IGCC co-production process can produce hydrogen while generating electric energy, solves the problem of refinery hydrogen source to a certain extent, and improves the hydrogenation economy. Subject to the Presence of H2Limitation of purification process, IGCC production of high purity H2Still face problems such as low efficiency, high cost, purification degree of difficulty, etc., how to further promote hydrogenation process efficiency becomes the research hotspot in recent years.
The conventional hydrogen purification techniques include Pressure Swing Adsorption (PSA), membrane separation, cryogenic separation, and the like. The PSA separation process usually requires multi-stage adsorption and desorption, but the adsorbent is difficult to regenerate, the investment cost is high, the operation is complex, and the economical efficiency is poor. Cryogenic separation has great energy consumption. The membrane separation technology has been rapidly developed in recent decades due to its obvious advantages of low investment cost, simple operation, high separation efficiency, small occupied area and the like.
Disclosure of Invention
The invention aims to provide a system for coupling hydrogen purification and wax oil hydrogenation in coal hydrogen production, which is used for separating and purifying hydrogen, carbon dioxide and hydrogenation recycle hydrogen in the coal hydrogen production based on a membrane separation technology. The high coupling of hydrogen production and hydrogenation is realized, the device investment is saved, and the hydrogenation efficiency is improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a system for hydrogen purification and wax oil hydrogenation coupling in coal hydrogen production comprises a carbon dioxide separation unit, a hydrogen purification unit, a wax oil hydrofining unit and an oil-gas separation unit;
the carbon dioxide separation unit comprises a precision filter 3, a No. 1 buffer tank 4, a No. 1 carbon membrane separator 5, a No. 1 compressor 6, a No. 1 cooler 7, a No. 2 carbon membrane separator 8 and a carbon dioxide product compressor 9 which are connected in sequence; the carbon dioxide separation unit is positioned at the beginning of the system and is used for separating carbon dioxide from the converted gas; cooling the coal hydrogen production conversion gas to 5-35 ℃ in a feed gas cooler 1, enabling the pressure to be 2-5 MPa, discharging water in a liquid separation tank 2, enabling the water to enter a precision filter 3 to filter dust and water vapor, and ensuring that the gas entering a carbon membrane separator is pure, wherein the molar concentration of hydrogen is 50-58% and the molar concentration of carbon dioxide is 35-42%; after being separated by a No. 1 carbon membrane separator 5, the carbon dioxide has the molar concentration of 60-65% and the pressure of 200-600 kPa, and is further compressed and cooled by a No. 1 compressor 6 and a No. 1 cooler 7; the molar concentration of the carbon dioxide subjected to secondary separation by a No. 2 carbon membrane separator 8 reaches over 90.00 percent, and the carbon dioxide compressed to 11-15 MPa by a carbon dioxide product compressor 9 enters a carbon dioxide conveying pipeline to prepare dry ice or is directly used as an oil displacement agent to be sealed underground;
the hydrogen purification unit comprises a No. 2 buffer tank 10, a No. 2 cooler 11, a hydrogen membrane separator 12, a No. 1 hydrogen sulfide removal stripping tower 13 and a hydrogen product compressor 14 which are connected in sequence; the hydrogen purification unit is positioned behind the carbon dioxide separation unit, and the residual gas produced by the No. 1 carbon membrane separator 5 of the carbon dioxide separation unit is mixed with the recycle hydrogen separated from the cold high-pressure separator 23 of the oil-gas separation unit in the No. 2 buffer tank 10; wherein the molar concentration of hydrogen in the residual gas produced by the No. 1 carbon membrane separator 5 is 85-89%, the molar concentration of circulating hydrogen in the oil-gas separation unit is 90-96%, the molar concentration of the mixed hydrogen is 91-94%, and the temperature is 300-350 ℃; after entering a hydrogen membrane separator 12 and sequentially passing through a No. 2 cooler 11 and a No. 1 hydrogen sulfide removal stripping tower 13, cooling a permeable gas hydrogen product to 55-75 ℃, desulfurizing and decarbonizing the permeable gas hydrogen product to reach a molar concentration of 99.5-99.9%, and entering a wax oil hydrorefining unit or directly entering a hydrogen network after passing through a hydrogen product compressor 14;
the wax oil hydrorefining unit comprises a fresh hydrogen compressor 15 and a fresh hydrogen heater 16 which are connected in sequence, and an oil pressure pump 17, a heating furnace 18, a hydrorefining reactor 19 and a hydrodesulfurization reactor 20 which are connected in sequence; the wax oil hydrorefining unit is positioned behind the hydrogen purification unit, the pressure of new hydrogen is 200-600 kPa, the new hydrogen is compressed to 8-13 MPa after passing through a new hydrogen compressor 15 and a new hydrogen heater 16, and after being cooled to 60-70 ℃, one path of the new hydrogen is mixed with wax oil and enters a hydrorefining reactor 19, and the other path of the new hydrogen is mixed with refined wax oil and enters a hydrodesulfurization reactor 20; after sequentially passing through an oil pressure pump 17 and a heating furnace 18, the wax oil is mixed with hydrogen from a hydrogen purification unit at the temperature of 300-400 ℃ and then enters a hydrofining reactor 19 for hydrogenation reaction; the main reaction process comprises the following steps:
(1) hydrodenitrogenation reaction
Non-heterocyclic compounds R-NH2+H2→RH+NH3
Non-basic heterocyclic nitrides
Basic heterocyclic nitrides
(2) Hydrodeoxygenation reaction
(3) Hydrodesulfurization reaction
Mercaptan RSH + H2→RH+H2S
Thioether RSR + H2→RSH+RH+H2→RSH+H2S
Disulfide RSSR + H2→2RSH2→RH+H2S+H2→RSR+H2S
Thiophene(s)
(4) Olefin and aromatic hydrogenation saturation reaction
R-CH＝CH2+H2→R-CH2-CH3
The oil-gas separation unit comprises a deamination gas stripping tower 21, a hot high-pressure separator 22 and a cold high-pressure separator 23 which are connected in sequence, and a hot low-pressure separator 24 and a No. 2 hot low-pressure gas dehydrogenation stripping tower 25 which are connected in sequence; the oil-gas separation unit is positioned at the tail end of the system and is closely connected with the hydrogen purification unit; firstly, removing ammonia gas in the hydrofined oil product through a deamination gas stripping tower 21, then respectively passing through a hot high-pressure separator 22, respectively entering a cold high-pressure separator 23 and a hot low-pressure separator 24 for treatment, and then separating oil, gas and water in the oil product according to the difference of pressure and temperature gradient, wherein the high pressure is 8-13 MPa, the low pressure is 6-8 MPa, the high temperature is 300-400 ℃, and the low temperature is 45-65 ℃; after the FCC raw oil is separated by the cold high-pressure separator 23, the cold high-pressure gas is the circulating hydrogen with the molar concentration of 95.48 percent, and returns to the hydrogen purification unit to be mixed with the residual gas of the No. 1 carbon membrane separator 5 for hydrogen purification; the hot low-fraction oil separated from the hot low-pressure separator 24 is sent to a fractionating tower to separate crude gasoline, and the hot low-fraction gas enters a No. 2 hot high-fraction gas hydrogen sulfide removal stripping tower 25 to remove hydrogen sulfide and simultaneously discharge sewage.
The membrane separator uses hollow fiber membrane or flat membrane as membrane material.
The hollow fiber membrane or the flat membrane is an organic membrane, an inorganic membrane or a composite membrane.
The invention has the beneficial effects that: on one hand, the membrane separation technology can obviously reduce the equipment investment of the traditional PSA separation and save the operation cost; the device occupies small area; the operation is simple and easy to control. On the other hand, the recycle hydrogen enters the hydrogen membrane separator, so that the traditional recycle hydrogen purification unit is omitted, the traditional flow is greatly simplified, and the device investment and the operation cost are reduced; the hydrogenation purity is improved, so that the hydrogenation efficiency is improved; the hydrogen partial pressure is reduced, thereby reducing the operating costs.
Drawings
FIG. 1 is a schematic diagram of the system of the present invention;
in the figure: 1 a feed gas cooler; 2, separating the liquid into liquid tanks; 3, a precision filter; 4 # 1 buffer tank; 5 # 1 carbon film separator; 6 # 1 compressor; 7 # cooler 1; 8 # 2 carbon film separator; 9 a carbon dioxide product compressor; 10 # 2 buffer tank; 11 # 2 cooler, 12 hydrogen membrane separator; 13 # 1 hydrogen sulfide removal stripper; 14 a hydrogen product compressor; 15 fresh hydrogen compressor; 16 fresh hydrogen heaters; 17 an oil pressure pump; 18 heating furnace; 19 a hydrofining reactor; 20 a hydrodesulfurization reactor; a 21 deamination gas stripping tower; 22 a hot high pressure separator; 23 a cold high pressure separator; 24 hot low pressure separator; 25 # 2 hot high-pressure gas-separation hydrogen sulfide removal stripping tower.
Detailed Description
The present invention is described in further detail below with reference to the attached drawing figures. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Referring to fig. 1, the system of the present invention includes a carbon dioxide separation unit, a hydrogen purification unit, a wax oil hydrorefining unit, and an oil-gas separation unit;
the carbon dioxide separation unit is positioned at the beginning of the system, firstly, the coal hydrogen production conversion gas is cooled to 25 ℃ from 300 ℃, the pressure is 3MPa, water is discharged from the liquid separation tank and then enters the precision filter, dust, water vapor and the like are filtered, the purity of the gas entering the membrane separator is ensured, and at the moment, the hydrogen molar concentration is 55.12%, and the carbon dioxide molar concentration is 40.02%. After separation in No. 1 carbon membrane separator, the carbon dioxide has a molar concentration of 62.25% and a pressure of 300kPa, so that further compression is required for the second stage separation. The molar concentration of the carbon dioxide passing through the No. 2 carbon membrane separator is 90.00 percent or more, the carbon dioxide is compressed to 15MPa and then enters a carbon dioxide conveying pipeline to prepare dry ice or is directly used as an oil displacement agent to be sealed underground.
The hydrogen purification unit is positioned after the carbon dioxide separation unit, the molar concentration of hydrogen in the No. 1 carbon membrane residual gas after the carbon dioxide separation of the raw material gas is 88.45 percent, and the molar concentration of circulating hydrogen in the oil-gas separation unit is 95.48 percent at the moment, the molar concentration of hydrogen after mixing is 93.81 percent, and the temperature is 320 ℃. Cooling to 75 ℃ before entering a hydrogen membrane separator, leading the hydrogen product of the permeation gas to have the molar concentration of 99.9 percent after desulfurization and decarburization, and entering a wax oil hydrorefining unit or a hydrogen network.
The wax oil hydrorefining unit is positioned behind the hydrogen purification unit, the pressure of new hydrogen is 300kPa, the new hydrogen needs to be compressed to 12MPa, and the wax oil hydrorefining unit enters the reactor after being cooled to 65 ℃. Wax oil is mixed with hydrogen from a hydrogen purification unit through an oil pressure pump and a heating furnace at the temperature of 370 ℃ and then enters a reactor for hydrogenation reaction.
The oil-gas separation unit is positioned at the tail end of the system and is closely connected with the hydrogen purification unit. Firstly removing ammonia gas in the oil product after hydrofining, then respectively separating oil, gas and water in the oil product by a hot high-temperature separation device, a cold high-temperature separation device and a hot low-temperature separation device according to different pressures and temperature gradients, wherein the high pressure is 12MPa, the low pressure is 6MPa, the high temperature is 378 ℃, and the low temperature is 65 ℃. And (3) after air cooling of the hot high-molecular gas, entering a cold high-molecular device, separating FCC raw oil, returning the cold high-molecular gas, namely circulating hydrogen with the molar concentration of 95.48 percent, to a hydrogen purification unit, and mixing the cold high-molecular gas with the residual gas of the No. 1 carbon membrane separator for hydrogen purification.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A system for hydrogen purification and wax oil hydrogenation coupling in coal hydrogen production is characterized by comprising a carbon dioxide separation unit, a hydrogen purification unit, a wax oil hydrofining unit and an oil-gas separation unit;
the carbon dioxide separation unit comprises a precision filter (3), a No. 1 buffer tank (4), a No. 1 carbon membrane separator (5), a No. 1 compressor (6), a No. 1 cooler (7), a No. 2 carbon membrane separator (8) and a carbon dioxide product compressor (9) which are connected in sequence; the carbon dioxide separation unit is positioned at the beginning of the system and is used for separating carbon dioxide from the converted gas; cooling the coal hydrogen conversion gas to 5-35 ℃ in a feed gas cooler (1), enabling the pressure to be 2-5 MPa, discharging water in a liquid separation tank (2), enabling the water to enter a precision filter (3) to filter dust and water vapor, and ensuring that the gas entering a carbon membrane separator is pure, wherein the molar concentration of hydrogen is 50-58% and the molar concentration of carbon dioxide is 35-42%; after being separated by a No. 1 carbon membrane separator (5), the carbon dioxide has the molar concentration of 60-65% and the pressure of 200-600 kPa, and is further compressed and cooled by a No. 1 compressor (6) and a No. 1 cooler (7); the molar concentration of carbon dioxide subjected to secondary separation by a No. 2 carbon membrane separator (8) reaches over 90.00 percent, and the carbon dioxide compressed to 11-15 MPa by a carbon dioxide product compressor (9) enters a carbon dioxide conveying pipeline to prepare dry ice or is directly used as an oil displacement agent to be sealed underground;
the hydrogen purification unit comprises a No. 2 buffer tank (10), a No. 2 cooler (11), a hydrogen membrane separator (12), a No. 1 hydrogen sulfide removal stripping tower (13) and a hydrogen product compressor (14) which are connected in sequence; the hydrogen purification unit is positioned behind the carbon dioxide separation unit, and the residual gas produced by a No. 1 carbon membrane separator (5) of the carbon dioxide separation unit is mixed with the circulating hydrogen separated from a cold high-pressure separator (23) of the oil-gas separation unit in a No. 2 buffer tank (10); wherein, the molar concentration of hydrogen in the residual gas produced by the No. 1 carbon membrane separator (5) is 85-89%, the molar concentration of circulating hydrogen in the oil-gas separation unit is 90-96%, the molar concentration of the mixed hydrogen is 91-94%, and the temperature is 300-350 ℃; after entering a hydrogen membrane separator (12) and sequentially passing through a No. 2 cooler (11) and a No. 1 hydrogen sulfide removal stripping tower (13), a permeable gas hydrogen product is cooled to 55-75 ℃, is desulfurized and decarbonized, then enters a wax oil hydrofining unit or enters a hydrogen network after passing through a hydrogen product compressor (14), and the molar concentration of the permeable gas hydrogen product is 99.5-99.9%;
the wax oil hydrorefining unit comprises a fresh hydrogen compressor (15) and a fresh hydrogen heater (16) which are connected in sequence, and an oil hydraulic pump (17), a heating furnace (18), a hydrorefining reactor (19) and a hydrodesulfurization reactor (20) which are connected in sequence; the wax oil hydrorefining unit is positioned behind the hydrogen purification unit, the pressure of new hydrogen is 200-600 kPa, after passing through a new hydrogen compressor (15) and a new hydrogen heater (16), the new hydrogen is compressed to 8-13 MPa, after being cooled to 60-70 ℃, one path of the new hydrogen is mixed with wax oil and enters a hydrorefining reactor (19), and the other path of the new hydrogen is mixed with refined wax oil and enters a hydrodesulfurization reactor (20); wax oil sequentially passes through an oil pressure pump (17) and a heating furnace (18), is mixed with hydrogen from a hydrogen purification unit at the temperature of 300-400 ℃, and then enters a hydrofining reactor (19) for hydrogenation reaction;
the oil-gas separation unit comprises a deamination gas stripping tower (21), a hot high-pressure separator (22), a cold high-pressure separator (23), a hot low-pressure separator (24) and a No. 2 hot low-pressure gas dehydrogenation stripping tower (25) which are connected in sequence; the oil-gas separation unit is positioned at the tail end of the system and is closely connected with the hydrogen purification unit; firstly, removing ammonia gas in an oil product after hydrofining through a deamination gas stripping tower (21), then respectively passing through a hot high-pressure separator (22), respectively entering a cold high-pressure separator (23) and a hot low-pressure separator (24) for treatment, and then separating oil, gas and water in the oil product according to different pressure and temperature gradients, wherein the high pressure is 8-13 MPa, the low pressure is 6-8 MPa, the high temperature is 300-400 ℃, and the low temperature is 45-65 ℃; after FCC raw oil is separated by the cold high-pressure separator (23), the cold high-pressure gas is circulating hydrogen with the molar concentration of 95.48 percent, returns to the hydrogen purification unit, and is mixed with the residual gas of the No. 1 carbon membrane separator (5) for hydrogen purification; the hot low-pressure oil separated in the hot low-pressure separator (24) is sent to a fractionating tower to separate crude gasoline, and the hot low-pressure gas enters a No. 2 hot high-pressure gas hydrogen sulfide removal stripping tower (25) to remove hydrogen sulfide and simultaneously discharge sewage.
2. The system for hydrogen purification and wax oil hydrogenation coupling in hydrogen production from coal as claimed in claim 1, wherein the membrane separator uses hollow fiber membrane or flat sheet membrane.
3. The system for hydrogen purification and wax oil hydrogenation coupling in coal-to-hydrogen as claimed in claim 2, wherein the hollow fiber membrane or flat sheet membrane is an organic membrane, an inorganic membrane or a composite membrane.
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| CN111378492B (en) * | 2018-12-28 | 2021-06-04 | 中国石油化工股份有限公司 | Heavy oil hydrogenation system and method capable of generating hydrogen by itself |
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| CN101338231A (en) * | 2006-05-03 | 2009-01-07 | 深圳市星原燃气轮机维修开发有限公司 | Natural gas or hydrogen gas made from coal |
| CN104152166A (en) * | 2014-06-11 | 2014-11-19 | 华南理工大学 | Comprehensive utilization system and process for hydrogen production by gasification of oil shale refining integrated associated coal |
| CN107629816A (en) * | 2016-07-18 | 2018-01-26 | 中国石化工程建设有限公司 | A kind of Heavy oil hydrogenation method |
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| CN101338231A (en) * | 2006-05-03 | 2009-01-07 | 深圳市星原燃气轮机维修开发有限公司 | Natural gas or hydrogen gas made from coal |
| CN104152166A (en) * | 2014-06-11 | 2014-11-19 | 华南理工大学 | Comprehensive utilization system and process for hydrogen production by gasification of oil shale refining integrated associated coal |
| CN107629816A (en) * | 2016-07-18 | 2018-01-26 | 中国石化工程建设有限公司 | A kind of Heavy oil hydrogenation method |
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