CN108165294A - A kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method - Google Patents
A kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method Download PDFInfo
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- CN108165294A CN108165294A CN201611151607.5A CN201611151607A CN108165294A CN 108165294 A CN108165294 A CN 108165294A CN 201611151607 A CN201611151607 A CN 201611151607A CN 108165294 A CN108165294 A CN 108165294A
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- Prior art keywords
- hydrogenation
- hydrogen
- coal
- oil
- hydrogen supply
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 722
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 722
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 672
- 238000000034 method Methods 0.000 title claims abstract description 458
- 239000003245 coal Substances 0.000 title claims abstract description 381
- 238000003723 Smelting Methods 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 594
- 239000003921 oil Substances 0.000 claims abstract description 538
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 361
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 358
- 239000007789 gas Substances 0.000 claims abstract description 285
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 277
- 239000002904 solvent Substances 0.000 claims abstract description 236
- 238000006243 chemical reaction Methods 0.000 claims abstract description 231
- 238000000926 separation method Methods 0.000 claims abstract description 221
- 239000007788 liquid Substances 0.000 claims abstract description 95
- 102220064512 rs577173144 Human genes 0.000 claims abstract description 69
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000003250 coal slurry Substances 0.000 claims abstract description 42
- 102200140294 rs137853257 Human genes 0.000 claims abstract description 26
- 239000007924 injection Substances 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims description 330
- 239000000047 product Substances 0.000 claims description 200
- 238000009835 boiling Methods 0.000 claims description 160
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 105
- 239000003054 catalyst Substances 0.000 claims description 103
- 239000002243 precursor Substances 0.000 claims description 95
- 238000012986 modification Methods 0.000 claims description 84
- 230000004048 modification Effects 0.000 claims description 84
- 239000000463 material Substances 0.000 claims description 47
- 230000000694 effects Effects 0.000 claims description 46
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 40
- 238000005243 fluidization Methods 0.000 claims description 39
- 238000010494 dissociation reaction Methods 0.000 claims description 38
- 230000005593 dissociations Effects 0.000 claims description 37
- 238000000197 pyrolysis Methods 0.000 claims description 33
- 239000007791 liquid phase Substances 0.000 claims description 25
- 238000012545 processing Methods 0.000 claims description 25
- 102220095091 rs10254120 Human genes 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 230000008859 change Effects 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006011 modification reaction Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000012805 post-processing Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000002817 coal dust Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000007667 floating Methods 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- -1 salt compound Chemical class 0.000 claims description 9
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 8
- 239000003034 coal gas Substances 0.000 claims description 8
- 230000003247 decreasing effect Effects 0.000 claims description 8
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 230000001839 systemic circulation Effects 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052683 pyrite Inorganic materials 0.000 claims description 7
- 239000011028 pyrite Substances 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 238000004227 thermal cracking Methods 0.000 claims description 7
- 229910017709 Ni Co Inorganic materials 0.000 claims description 6
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 6
- 239000003426 co-catalyst Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 102200160920 rs35304565 Human genes 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 19
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 239000011949 solid catalyst Substances 0.000 description 8
- 230000004087 circulation Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000015220 Febrile disease Diseases 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009422 external insulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 238000007616 round robin method Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method, non- coal derived oils are converted by online solvent oil hydrogenation modified-reaction process R30 with the hydrocarbon ils that the oily coal of press-in after coal slurry is refined altogether in the hot gas separated by high pressure separator R10P HS V of hydrogenation process R10 products therefroms R10P and the product R30P comprising gas phase R30P V and oil phase R30P L are separated into comprising R30P, logistics of at least part comprising oil phase R30P L enters R10 and recycles hydrogen supply agent SR LBDS as short route, and low cost manufacturing goes out " rich reactive hydrogen " reaction condition;Enter R10 in a manner of from pressure into preposition R30 products therefroms after the warm high score oil R10P MS L of R10P HS V are pressurizeed, flow is more terse;R10 can use gas-liquid separation process between high concentration coal, pre-add hydrogen section, grade, classify in batches injection hydrogen supply dissolvent, product to use the hot high score of hydrogen gas stripping type.
Description
Technical field
The present invention relates to a kind of oily coals with short cycle hydrogen supply dissolvent oil to be total to smelting method, and non-coal derived oils are pressed into after matching coal slurry
The hydrocarbon ils that oily coal is refined altogether in the hot gas separated by high pressure separator R10P-HS-V of hydrogenation process R10 products therefroms R10P passes through online solvent naphtha
Hydrogenation modification reaction process R30 is converted into is separated into the product R30P comprising gas phase R30P-V and oil phase R30P-L comprising R30P,
Logistics of at least part comprising oil phase R30P-L enters R10 and recycles hydrogen supply agent SR-LBDS as short route, and low cost manufacturing goes out
" rich reactive hydrogen " reaction condition;Will R10P-HS-V warm high score oil R10P-MS-L pressurize after enter preposition R30 products therefroms with
Enter R10 from pressure mode, flow is more terse;R10 can use gas-liquid separation process between high concentration coal, pre-add hydrogen section, grade, divide
Criticize classification injection hydrogen supply dissolvent, product uses the hot high score of hydrogen gas stripping type.
Background technology
Oily coal refines altogether, refers to simultaneously carrying out coal and non-coal derived oils common processing.
Hydrogen supply hydrocarbon described herein refers to thering is the hydrocarbon component of hydrogen supply in the direct liquefaction reaction process of coal hydrogenation,
The polycyclic aromatic hydrocarbon of double ring arene of the hydrogen supply hydrocarbon including fractional saturation, fractional saturation, is the confession that direct hydrogenation liquefaction of coal process uses
The ideal composition of hydrogen solvent naphtha.In hydrogen supply hydrocarbon, the hydrogen supply speed of dihydro body is all higher than tetrahydrochysene body, the dihydro body of thrcylic aromatic hydrocarbon and double
The dihydro body of cycloaromatics is compared, and it is low that hydrogen supply speed has height to have;Although experiment it has been proved that polycyclic aromatic hydrocarbon without hydrogen supply capacity,
There is the ability for transmitting hydrogen.At 400 DEG C, the opposite hydrogen supply speed of following component is as follows:
Hydrogen supply dissolvent oil, refers to the hydrocarbon ils rich in hydrogen supply hydrocarbon.
Smelting method is total to about existing oily coal, a document for recording this kind of data is shown in document A01:1. publication title:
《Modern Coal-based Chemical technical manual》, page 1060 to page 1063;2. retrieval is encoded with books:ISBN is encoded:978-7-122-
09636-4, Chinese depository library CIP data cores word (2010) the 197010th;3. it writes:He Yongde is edited;4. publishing house:
Chemical Industry Press.
Oily coal refines the high boiling substance of feedstock oil AF used in process, typically low value altogether, such as comes from PETROLEUM PROCESSING
Pitch, extra-heavy crude oil or the petroleum residue of industry or tar liquid hydrocarbon.
Oily coal refines process altogether, and feedstock oil AF is used for preparing coal slurry and the pumped (conveying) medium as coal, but without hydrogen supply dissolvent
Oil return line, basic technology can be single hop or two sections.Refine process altogether in oily coal, most of fluid product from derived from oil rather than
It is made from coal, certain small part fluid product is made from from coal.Oily coal refines process altogether, and general objective is by stone while coal liquefaction
Oily derivative upgrading reduces investment and the operating cost of unit product.But non-coal derive solvent to the solubility property of coal compared with
Difference, hydrogen supply capacity liquid is very low, and therefore, the development of evil in febrile disease rate for not being converted into fluid product is relatively low.
In fact, oily coal be total to the research history of sweetening process more than 45 years, but so far still commercial-free plant construction with
It goes into operation.
Existing oil coal refines process for selective hydrogenation altogether, in order to realize the target of Low investment and low operating cost, not use
Condition premised on cycle hydrogen supply dissolvent;And hydrogenation process is refined altogether in oily coal, stablizing for the free radical that coal liquefaction generates needs
A large amount of reactive hydrogens, stablizing for the free radical that feedstock oil thermal cracking generates need a large amount of reactive hydrogens, deviate from miscellaneous element such as oxygen, sulphur, nitrogen
Plus hydrogen dissociation reaction need a large amount of reactive hydrogens, the wilderness demand of reactive hydrogen, refining hydrogenation process altogether with oily coal can not provide
The essential contradiction that can not be balanced is formed between the inherent characteristics of a large amount of activity, it is high to lack macromolecular hydrocarbon under the reaction condition of reactive hydrogen
Warm condensation reaction largely generates a large amount of thermal condensation object such as coke, and therefore, oily coal refines hydrogenation process or conversion altogether
Rate is extremely low, and improves conversion ratio then a large amount of coking reaction process can not long-time continuous operation.
As seen from the above analysis, the essential defect that existing oily coal refines process for selective hydrogenation altogether is not providing anti-
In requisition for a large amount of reactive hydrogens, two by using can be released effectively reactive hydrogen hydrogen supply dissolvent oil, can significantly improve existing
Oily coal refine process for selective hydrogenation altogether, still, if big followed using be similar to that the direct liquefaction process of existing coal hydrogenation uses
Hydrogen supply dissolvent oil is used for preparing coal slurry and pumped (conveying) medium as coal, then oily coal can be caused to refine altogether by ring hydrogen supply dissolvent oil return line
The investment of the unit product of overall process and operating cost significantly rise, and lose economic competitiveness.
In fact, oily coal refines process altogether, feedstock oil AF is used for preparing coal slurry and the pumped (conveying) medium as coal, therefore and be not required to
Hydrogen supply dissolvent oil keeper load is wanted to prepare the task of coal slurry and the pumped (conveying) medium as coal, only needs to undertake that " conveying quantity is sufficient
The function of reactive hydrogen ", based on the analysis, present invention contemplates that proposition is a kind of to refine hydrogenation process conveying hydrogen supply dissolvent altogether to oily coal
The cost effective method of oil is to produce " rich reactive hydrogen " reaction condition, since the recycled solvent oil of system cycle hydrogen supply dissolvent adds hydrogen steady
It is necessary step to determine reaction process and the defeated step of cycle containing hydrogen-containing hydrocarbon stream, and therefore, it is an object of the present invention to how build most
Terse circulation process.And the hydrogen supply dissolvent oil carrying method used for reference can be supplied, mostly come from direct hydrogenation liquefaction of coal process
Hydrogen supply dissolvent oil carrying method.Direct hydrogenation liquefaction of coal process refers to the hydrogen supply dissolvent produced simultaneously to coal and coal derived oils
The Coal Liquefaction process that oil carries out.
Hydrogen supply dissolvent oil and its carrying method that direct hydrogenation liquefaction of coal process uses is described below.
In direct hydrogenation liquefaction of coal reaction process, hydrogen supply dissolvent is substantially a kind of the most important of coal liquefaction positive reaction
Foreground catalyst, he quickly provides most of reactive hydrogen of coal liquefaction, it directly decides pyrolysis free radical fragment
The speed that flash hydrogcnation is stablized, thus thermal condensation is inhibited to react;In direct hydrogenation liquefaction of coal reaction process, solid catalyst
Such as pyrite, molybdenum sulfide are substantially a kind of retarding agents of coal liquefaction negative reaction, and solid catalyst particle absorption viscosity is big
Colloid, asphaltene molecules MK, and MK is made to be contacted with the reactive hydrogen of solid catalyst surface, so as to inhibit its pyrocondensation;In coal hydrogenation
In direct liquefaction reaction process, solid catalyst such as pyrite, molybdenum sulfide etc. substantially simultaneously or a kind of hydrogen supply agent dehydrogen substance
The recovery catalyst of SH-Z, solid catalyst particle absorption SH-Z, and SH-Z is made to be contacted with the reactive hydrogen of solid catalyst surface,
So as to which hydrogen be added to be restored to the hydrogen supply hydrocarbon for having hydrogen supply capacity, it directly decides the recovery speed of hydrogen supply agent dehydrogen substance SH-Z;
In direct hydrogenation liquefaction of coal reaction process, substantially still a kind of target is hydrocracked anti-solid catalyst such as pyrite etc. simultaneously
It should be such as asphaltene, the weak action catalysts being hydrocracked of preasphaltene.Therefore, in direct hydrogenation liquefaction of coal reaction process,
In certain sense, solid catalyst such as pyrite, molybdenum sulfide etc. is more like a kind of catalyst of backstage running, to coal liquefaction
Target product distillate plays a kind of support property and the effect of promotion property.In coal hydrogenation liquefaction reaction process KR10, due to hydrogen supply
The effect of solvent DS is extremely important, and therefore, the operating condition and effect of solvent oil hydrogenation stabilization reaction process are naturally of crucial importance.
About existing direct hydrogenation liquefaction of coal technique and hydrogen supply dissolvent round-robin method, a document of this kind of data is recorded
See document A01:1. publication title:《Coal direct liquefaction technique and engineering》, page 130 to page 365;2. retrieval is compiled with books
Code:ISBN is encoded:9-78703-04308-23;3. it writes:Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin;4. publishing house:Science
Publishing house.
The online solvent oil hydrogenation modified-reaction process of existing direct hydrogenation liquefaction of coal technique is reacted with coal hydrogenation liquefaction
The flow relationship of process KR10, is divided into the off-line type i.e. solvent oil hydrogenation antihunt means of separate high pressure system and postposition is online i.e.
Solvent oil hydrogenation steady decrease investment and energy are carried out by the high-pressure system of the hot gas separated by high pressure separator of secondary use KR10 products KR10P
Consumption;Off-line type stabilized hydrogenation method good product quality but investment is big, can not be adopted by the present invention;And postposition it is online plus
The investment of stabilized hydrogen method is saved but there is by the H in KR10 products2O、NH3、H2S、CO、CO2, HCL introduce stabilized hydrogenation
Reaction process so as to deteriorate the catalyst of hydrogen supply dissolvent stabilized hydrogenation reaction process operation efficiency (cause catalyst life it is short, supply
Hydrogen solvent quality is unstable) significant deficiency, can not also be adopted by the present invention.
The solvent oil hydrogenation of existing direct hydrogenation liquefaction of coal technique stablizes the cycle side of hydrogen supply dissolvent obtained by reaction product
Method, is that separation stabilized hydrogenation reaction product obtains the hydrogen supply dissolvent of low pressure, is then prepared under lower pressure as coal slurry molten
Agent uses, this systemic circulation flow, and flow is complicated, step is more, investment is high, energy consumption is big, the residence time is long, hydrogen supply dissolvent property is easy
In variation (mainly partial lose effective hydrogen supply capacity), if realizing that cost is huge if " the sufficient hydrogen supply dissolvent of quantity "
Greatly.In fact, as high concentration coal is prepared, the long-term industry chemical conversion work(of conveying technology operates, part hydrogen supply dissolvent is complete
The direct liquefaction reaction process KR10 of coal hydrogenation can be directly entered under high pressure and higher temperature conditions without by being depressured, dividing
From, with coal slurry, coal slurry pressurized delivered, coal slurry high pressure preheating and etc., formed part hydrogen supply dissolvent short route cycle, low cost
Produce " rich reactive hydrogen " reaction condition.
According to above-mentioned concept, can occur using hydrocarbon ils in hot gas separated by high pressure separator KR10P-HS-V as the short recycled solvent oil of precursor
Hydrogenation modification reaction process R30 hydrogenation process R30, while there may be evaporated with heat of dissociation high score oil KR10P-HS-L gained
Point oil is the long circulating solvent oil hydrogenation modified-reaction process R20 of precursor, and certainly, the operation with high pressure step of R30 and R20 can be with
Part merges with simple flow, and the portion of product solvent naphtha of R30 or R20 can serve as the dispensing of coal.
On the other hand, the solvent oil hydrogenation of existing direct hydrogenation liquefaction of coal technique stablizes hydrogen supply dissolvent obtained by reaction product
It is to match hydrogen supply agent with coal slurry from reaction initiating terminal injection into the addition point of direct hydrogenation liquefaction of coal reaction process KR10
The mode of material enters, and can not realize " hydrogen supply dissolvent is dispersed in all reaction compartments ".
Analysis below low boiling dot cycle hydrogen supply agent LBDS and height boiling dot cycle hydrogen supply agent LBDS.
Low boiling dot cycle hydrogen supply agent LBDS described herein refers to normal boiling point between 250~400 DEG C of hydrogen supply hydrocarbon, master
To be 2 rings, 3 rings, 4 ring structure hydrocarbon.Height boiling dot cycle hydrogen supply agent HBDS described herein, refers to normal boiling point between 400~530
DEG C hydrogen supply hydrocarbon, predominantly 4 rings, 5 ring structure hydrocarbon.
Relative to higher boiling hydrogen supply agent HBDS, LBDS when molecular weight is small difficult thermal cracking, because the small movement velocity of molecular weight is fast,
Because low boiling point while being easy to vaporization liquid Space residence time in KR10 is short and once become one way into gas phase and pass through, because dividing
Minor structure is preferable therefore hydrogen supply speed is fast, so with the high advantage of low pyrolysis rate, quick hydrogen supply, load hydrogen load.
It is i.e. hot because molecular weight die is easy to thermal cracking relative to low boiling dot cycle hydrogen supply agent LBDS, higher boiling hydrogen supply agent HBDS
Solve temperature it is low, because the big movement velocity of molecular weight it is slow, because boiling point it is high-leveled and difficult in vaporization due to KR10 liquid Space stay cycle
It is long, because its complicated hydrogen supply speed of molecular structure is slow, be easy to pyrocondensation and, so with high pyrolysis rate, high condensation produce rate, supplying at a slow speed
Hydrogen carries the low relative disadvantage of hydrogen load;But for the liquid phases the hydrocarbon component such as higher boiling free radical LC, higher boiling hydrogen supply agent
HBDS is the reliable liquid phase hydrogen supply agent of LC.
As seen from the above analysis, in order to which the coal conversion per pass of KR10, inhibition thermal condensation produce rate, raising product add
Hydrogen depth reduces KR10 reaction overall temperature rises, needs to be achieved at low cost that " the sufficient hydrogen supply dissolvent of quantity is dispersed in all anti-
Answer space ", the using priciple about hydrogen supply dissolvent oil, it should be:
1. in order to realize that low cost increases hydrogen supply agent quantity, the hydrogen supply agent recycle stream using the few low cost of step is needed
Journey, i.e. short circuit current journey;
2. in order to form the liquid-phase hydrogenatin reaction condition of " rich reactive hydrogen ", need to increase overall hydrogen supply agent quantity, in order to drop
The thermal cracking rate of low circulation hydrogen supply agent, it should increase low boiling dot cycle hydrogen supply agent LBDS quantity as far as possible, such as before KR10
Portion or central reaction zone increase low boiling dot cycle hydrogen supply agent LBDS dosages;
3. high-concentration coal slurry oil technology, the relatively low reaction using hydrogen migration liquid phase reactor ratio between reinforcing hydrocarbon molecule can be used
The pre-add hydrogen section of temperature, consumes the reactive hydrogen from low boiling dot cycle hydrogen supply agent LBDS;
4. implement segmentation injection low boiling dot cycle hydrogen supply agent LBDS, using gas-liquid separation process, part LBDS between grade rearward
Injection, product realize short route cycle using the hot high score mode of hydrogen gas stripping type;
5. part higher boiling hydrogen supply agent HBDS is introduced directly into KR10 rear portions reaction compartment, directly increases liquid phase and supply Hydrogen Energy
Power;
6. it can set or combine setting higher boiling hydrogen supply agent HBDS hydrogenation processes, particularly suitable for large-scale coal liquification device.
Document A01《Coal direct liquefaction technique and engineering》Page 214 to page 216 to describe hydrogen supply dissolvent stabilized hydrogenation anti-
The impurity of process and coal hydrogenation liquefaction reaction process KR10, the yield of carburet hydrogen are answered, sees Tables 1 and 2.
Table 1BSU coal direct liquefaction material balance tables
Project | Into/maf.wt% | Into/maf.wt% | Go out/maf.wt% | Go out/maf.wt% | Into-go 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 | 128.52 | 122.22 | 0.00 | 0.00 | -128.52 |
Oily (220 DEG C of <) | 0.00 | 0.00 | 25.33 | 24.09 | 25.33 |
Oily (220 DEG C of >) | 0.00 | 0.00 | 30.01 | 28.54 | 30.01 |
Solvent materials | 0.00 | 0.00 | 128.52 | 122.22 | 128.52 |
H2O | 0.00 | 0.00 | 12.27 | 11.67 | 12.27 |
538 DEG C or more fractions | 0.00 | 0.00 | 15.21 | 14.46 | 15.21 |
H2 | 5.65 | 5.37 | 0.00 | 0.00 | -5.65 |
Moisture-and-ash-free basis coal | 100.00 | 95.10 | 8.78 | 8.35 | -91.22 |
Ash | 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 |
Sulphur | 1.20 | 1.14 | 0.69 | 0.66 | -0.51 |
DMDS | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
It is total | 242.18 | 230.32 | 242.18 | 230.32 | 0.00 |
Table 2BSU solvent hydrogenation unit material balance tables
Project | Into/maf.wt% | Into/maf.wt% | Go out/maf.wt% | Go out/maf.wt% | Into-go 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 | 0.00 | 0.00 | 128.73 | 122.42 | 128.73 |
Oily (220 DEG C of <) | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Oily (220 DEG C of >) | 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 |
538 DEG C or more fractions | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
H2 | 1.16 | 1.11 | 0.00 | 0.00 | -1.16 |
Moisture-and-ash-free basis coal | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
Ash | 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 |
Sulphur | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
DMDS | 1.93 | 1.83 | 0.00 | 0.00 | -1.93 |
It is total | 131.61 | 125.16 | 131.61 | 125.16 | 0.00 |
For hydrogen supply dissolvent stabilized hydrogenation reaction process RX0 and coal hydrogenation liquefaction reaction process KR10, raw material impurity is contained
Amount, impurity hydrogenation conversion, gas Auditory steady-state responses carry out statistical comparison, can obtain drawing a conclusion:
1. liquefaction coal, typically miscellaneous the element such as high coal of oxygen, sulphur, nitrogen content, direct hydrogenation liquefaction of coal process are typically
The higher process of impurity conversion ratio, impurity composition such as H2O、NH3、H2S、CO、CO2Yield it is larger;
2. the high coal of liquefaction coal, the typically content of organic matter, direct hydrogenation liquefaction of coal process is typically organic matter liquefaction
The higher process of conversion ratio, conventional gas hydrocarbon such as CH4、C2、C3、C4Yield it is larger;
3. the raw material hydrocarbon of hydrogen supply dissolvent stabilized hydrogenation reaction process R20, typically miscellaneous element is as oxygen, sulphur, nitrogen content are low
Hydro carbons, direct hydrogenation liquefaction of coal process are typically the relatively low process of impurity conversion ratio, impurity composition such as H2O、NH3、H2S、CO、
CO2Yield it is smaller;
4. hydrogen supply dissolvent stabilized hydrogenation reaction process RX0, the typically relatively low process of cracking conversion rate, conventional gas hydrocarbon is such as
CH4、C2、C3、C4Yield it is smaller.
Based on above-mentioned conclusion, it is presently believed that using the extremely low new hydrogen of impurity concentration and/or the preposition solvent naphtha of recycle hydrogen
Stabilized hydrogenation reaction process, foreign gas therein, carburet hydrogen quantity are seldom, and therefore, solvent oil hydrogenation stablizes reaction process RX0
The separating obtained hot gas separated by high pressure separator RX0P-V of product RX0P can enter coal hydrogenation liquefaction reaction process KR10 and realize secondary effective profit
With.In this way, it can both avoid " by the H in R10 products2O、NH3、H2S、CO、CO2, HCL introduce stabilized hydrogenation reaction process RX0 from
And deteriorated catalyst operation efficiency " defective workmanship, while can realize the secondary use of circulating hydrogen again, forward type can be formed
Solvent oil hydrogenation stablizes reaction process RX0 and coal hydrogenation liquefaction reaction process KR10 combined methods, forms a kind of concise flow
Smelting method is total to the direct method for producing oil of coal or oily coal of short cycle hydrogen supply dissolvent oil.
In terms of from the application effect of known direct hydrogenation liquefaction of coal process catalyst or technique, large-scale or industrialization operating number
It is not so good as the data and working order of minitype high voltage stirred tank experimental rig according to such as liquefied coal coil yield, reactor operability,
Inventors believe that the basic reason for such difference occur is following reason, improved process can be formed by improving them:
1. in HV XLPE power cables reaction, the sufficient hydrogen supply dissolvent of quantity is dispersed in all reaction compartments, and industrial
Device does not accomplish this point anyway yet, can only carry out Approximation operation;
The direct hydrogenation liquefaction of coal process being currently known nearly all is to note hydrogen supply agent from reactor initial space end
Enter, entered in a manner of coal slurry dispensing;
2. in HV XLPE power cables reaction, gas phase reaction product can be rapidly separated liquid phase into superposed gas phase
In, almost no longer with liquid phase haptoreaction, and commercial plant does not accomplish this point anyway yet, can not set it is enough in
Between gas-liquid separator, gas-phase product is separated in time;Can only carry out Approximation operation;
The direct hydrogenation liquefaction of coal process being currently known, it is also difficult to simply realize intermediate gas-liquid separation operation, it will
Partial gas phase product is separated in time;Nearly all it is to discharge gas-liquid product from reactor end in a manner of cocurrent, gas phase is anti-
Answering product, haptoreaction is inevitable repeatedly with liquid phase;Intermediate product impurity such as H2O、NH3、H2S、CO、CO2, HCL presence, both
It reduces hydrogen partial pressure and poisons hydrogenation catalyst, also takes up reaction compartment volume;
3. in HV XLPE power cables reaction, contact of the catalyst granules with liquid phase material, high, the catalyst table that detaches frequency
The contacting efficiency of face and liquid phase molecule is high, and commercial plant does not accomplish this point anyway yet, can only carry out Approximation
Operation is that preferably fluidisation state strengthens stirring action, reduction catalyst to maintenance catalyst in the liquid phase as increased liquid phase circulation amount
Granularity increases catalyst dispersion degree.
So far, the basic imagination of the present invention has been formed:A kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method, non-
The oily coal of press-in is refined altogether in the hot gas separated by high pressure separator R10P-HS-V of hydrogenation process R10 products therefroms R10P after coal derived oils match coal slurry
Hydrocarbon ils be converted by online solvent oil hydrogenation modified-reaction process R30 and be separated into comprising R30P comprising gas phase R30P-V and oil
The product R30P of phase R30P-L, the logistics at least partially comprising oil phase R30P-L enter R10 and recycle hydrogen supply agent as short route
SR-LBDS, low cost manufacturing go out " rich reactive hydrogen " reaction condition;The warm high score oil R10P-MS-L pressurizations of R10P-HS-V is laggard
Enter preposition R30 products therefroms and enter R10 in a manner of from pressure, flow is more terse;R10 can use high concentration coal, pre-add hydrogen section,
Gas-liquid separation process, classify in batches injection hydrogen supply dissolvent, product use the hot high score of hydrogen gas stripping type between grade.
The method of the invention has not been reported.
In order to optimize effect of the present invention, group technology can be combined into other multiple technologies.
At least part low boiling hydrocarbon obtained by heat of dissociation high score oil R10P-HS-L can be introduced online solvent and add hydrogen steady
Determine reaction process RX0, Joint Production short route lightweight hydrogen supply hydrocarbon and with the long flow lightweight hydrogen supply hydrocarbon of coal slurry, at this moment, part heat
High score oil RX0P-HS-L enters separation/fractional distillation process and isolates with coal slurry lightweight hydrogen supply hydrocarbon.
The solvent oil hydrogenation of high boiling hydrocarbon HBML obtained by heat of dissociation high score oil R10P-HS-L can be stablized reaction process
R20 stablizes reaction process R30 with short route solvent oil hydrogenation, carries out the combination of high-pressure system, such as by high boiling hydrocarbon HBML's
Solvent oil hydrogenation stablizes a part for hot high score oil obtained by the high pressure hot separator of reaction process R20 products R20P, with short route
A part for hot high score oil, mixes obtained by the high pressure hot separator of online solvent hydrogenation process R30 products R30P
The initial hydrogenation liquefaction reaction process for entering R10 with coal slurry mixing hydrogen supply hydrocarbon is isolated into separation/fractional distillation process, simultaneously
The remainder of high score oil hot obtained by the high pressure hot separator of the online solvent hydrogenation process R30 products R30P of short route is separated
Enter the intermediate hydrogenation liquefaction reaction process of R10, while the solvent oil hydrogenation of high boiling hydrocarbon HBML is stablized into reaction process R20 products
The remainder of hot high score oil introduces the last hydrogenation liquefaction reaction process of R10 obtained by the high pressure hot separator of R20P, in this way, logical
Classification injection hydrogen supply dissolvent in batches is crossed, is rationally realized " the sufficient hydrogen supply dissolvent of quantity is dispersed in all reaction compartments ".
Rear-mounted online solvent oil hydrogenation stablizes reaction process R30, can be charging with hot gas separated by high pressure separator R10P-HS-V, can use
The cold oil of the warm high score process of hot gas separated by high pressure separator R10P-HS-V is charging, can use the warm high score process of hot gas separated by high pressure separator R10P-HS-V
Cold oil hydrogen air lift after oil be charging, other similar materials can be processed simultaneously, short cycle light recycle hydrogen supply agent SR-
Enter direct hydrogenation liquefaction of coal process R10 after LBDS pressurizations.
The online solvent hydrogenation process R30 of forward type can process the warm high score process of hot gas separated by high pressure separator R10P-HS-V
Liquid after the supercharging of cold oil, can process other similar materials simultaneously, and short cycle light recycle hydrogen supply agent SR-LBDS can be according to
Enter direct hydrogenation liquefaction of coal process R10 by pressure itself.
It can set or combine setting high boiling point solvent oil stabilized hydrogenation reaction process R30 production higher boiling hydrogen supply agent HBDS,
Processing carrys out the normal boiling point of self-heating high score oil R10P-HS-L between 200~530 DEG C of the hydrocarbon component.
Therefore, an object of the present disclosure is to propose that a kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method.
Second purpose of the invention is to propose that a kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method, is forward type solvent
Oily stabilized hydrogenation reaction process R30 refines hydrogenation process R10 combined methods altogether with oily coal.
The purpose of third of the present invention is to propose a kind of oil with short cycle hydrogen supply dissolvent oil of the injection hydrogen supply dissolvent of classification in batches
Coal is total to smelting method.
4th purpose of the invention is to propose that a kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method, can be added with a variety of coals
The direct liquefaction reaction method of hydrogen is applied in combination.
Invention content
A kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method, it is characterised in that comprises the steps of:
(1) it is made into coal R10F in coal process for preparation M10, feedstock oil SHVGO, the coal dust SF of non-coal derived oils;
(2) hydrogenation process R10 is refined altogether in oily coal, in short route recycled solvent oil SR-DS, hydrogen from step (4)
Gas, the oily coal that may be used are refined altogether under hydrogenation catalyst existence condition, and coal R10F is converted into coal and refines hydrogenation products R10P altogether;
Hydrogenation process R10 is refined altogether in oily coal, and the coal dust in coal R10F occurs the swelling of coal, pyrolysis, hydrogen added to split
The lightings such as thermal cracking, stabilized hydrogenation occur for the Coal liquefactions such as change, stabilized hydrogenation, the feedstock oil SHVGO in coal R10F
Reaction, short route recycled solvent oil SR-DS is at least to the effect of pyrolysis free radical release reactive hydrogen;
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V altogether
With hot high score oil R10P-HS-L;
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in short route recycled solvent oil hydrogenation modification
Reaction process R30 under hydrogen, short route recycled solvent oil hydrogenation catalyst existence condition, includes hot gas separated by high pressure separator R10P-HS-V
The hydrogen supply hydrocarbon precursor R30F of middle the hydrocarbon component occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into rich in hydrogen supply hydrocarbon
Reaction effluent R30P;
High pressure stream comprising the hydrocarbon component in reaction effluent R30P is used as short route recycled solvent oil SR-DS, into
Enter oily coal and refine hydrogenation process R10 altogether;
It is used as hydrogen-rich stream XH comprising the high pressure gas logistics for carrying out hydrogen in self-heating gas separated by high pressure separator R10P-HS-V;
(5) in post processing system R10P-HS-V-AUNIT, separation and recovery hydrogen-rich gas XH obtain hydrogen-rich gas XHV and
Hydrocarbon ils XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles.
The present invention, the 1st kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is that postposition is online plus hydrogen changes
Property method, hot gas separated by high pressure separator R10P-HS-V is directly entered reaction process R30, and setting short route recycles the hydrogenation modification reaction of solvent
Thermal high separation process R30P-HS, the delivery pump A-PUMP of process R30, R30 product R30P, comprises the steps of:
1. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, add hydrogen steady in hydrogen, short route hydrogen supply dissolvent oil
Determining under catalyst existence condition, hot gas separated by high pressure separator R10P-HS-V enters reaction process R30 and switchs to the product R30P rich in hydrogen supply hydrocarbon,
The reaction of at least part aromatic hydrogenation fractional saturation occurs for the hydrocarbon component that hot gas separated by high pressure separator R10P-HS-V is carried;
2. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH, the hot high score oil R30P-HS-L warps of at least part
Enter oily coal as logistics SR-DS after delivery pump A-PUMP pressurizations and refine hydrogenation process R10 altogether.
The present invention, the 2nd kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is that postposition is online plus hydrogen changes
Property method, hot gas separated by high pressure separator R10P-HS-V is in warm high score oil R10P- isolated warm high pressure separation process R10P-HS-V-MS
HS-V-MS-L enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, sets warm high pressure separation process R10P-HS-V-
MS, the thermal high separation process R30P- that short route recycles hydrogenation modification reaction process R30, the R30 product R30P of solvent is prepared
HS, delivery pump A-PUMP, comprise the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L;
Hot gas separated by high pressure separator R30P-HS-V is used as logistics XH at least partially;
2. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, add hydrogen steady in hydrogen, short route hydrogen supply dissolvent oil
Determine under catalyst existence condition, warm high score oil R10P-HS-V-MS-L enters reaction process R30 and is converted into the production rich in hydrogen supply hydrocarbon
The reaction of at least part aromatic hydrogenation fractional saturation occurs for object R30P, the hydrocarbon component that hot gas separated by high pressure separator R10P-HS-V is carried;
3. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH, the hot high score oil R30P-HS-L warps of at least part
Enter oily coal as logistics SR-DS after delivery pump A-PUMP pressurizations and refine hydrogenation process R10 altogether.
The present invention, the 3rd kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model changes for preposition online plus hydrogen
Property method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent plus hydrogen change
The thermal high separation process R30P-HS of property reaction process R30, R30 product R30P, comprises the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the predecessor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of object R30F, in hydrogen, there are items for short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst
The reaction of at least part aromatic hydrogenation fractional saturation occurs under part, is converted into the product R30P rich in hydrogen supply hydrocarbon;
4. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot high score oil R30P-HS-L of at least part enter oily coal as logistics SR-DS and refine hydrogenation process altogether
R10。
The present invention, the 4th kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model changes for preposition online plus hydrogen
Property method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent plus hydrogen change
The thermal high separation process R30P-HS of property reaction process R30, R30 product R30P, comprises the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the predecessor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of object R30F, in hydrogen, there are items for short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst
The reaction of at least part aromatic hydrogenation fractional saturation occurs under part, is converted into the product R30P rich in hydrogen supply hydrocarbon, at least part
Hot high score oil R30P-HS-L enters oily coal as logistics SR-DS and refines hydrogenation process R10 altogether.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process
R30P-HS can use liquid existing for air lift hydrogen R30P-HS-BV contact thermal high separation processes R30P-HS, with air lift
Low boiling component therein, gas stripping gas enter in hot gas separated by high pressure separator R30P-HS-V.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process
R30P-HS, hot high score oil R30P-HS-L are mainly made of hydro carbons of the normal boiling point higher than 280 DEG C or higher than 230 DEG C.
The present invention, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, thermal high separation process R30P-
The operation temperature of HS:Usually 150~330 DEG C, generally 180~280 DEG C, preferably 200~250 DEG C.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in warm high pressure separation process
R10P-HS-V-MS can use air lift hydrogen R10P-HS-V-MS-BV contacts temperature high pressure separation process R10P-HS-V-MS to deposit
Liquid, with air lift low boiling component therein, gas stripping gas may finally be entered in warm gas separated by high pressure separator R10P-HS-V-MS-V.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in warm high pressure separation process
R10P-HS-V-MS, warm high score oil R10P-HS-V-MS-L are mainly by hydro carbons group of the normal boiling point higher than 250 DEG C or higher than 200 DEG C
Into.
The present invention, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, warm high pressure separation process R10P-
The operation temperature of HS-V-MS:Usually 150~330 DEG C, generally 180~280 DEG C, preferably 200~250 DEG C.
The present invention, (1) quality of pc concentration in coal process for preparation M10, coal slurry R10F:Typically larger than 30%, one
As be more than 40%, more preferably greater than 45%.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, can set pre-hydrotreating reaction section R10-DD;
In pre-hydrotreating reaction section R10-DD, coal R10F occurs pre-hydrotreating reaction and is converted into the pre- hydrogenation products R10- of coal
DD-P, short route hydrogen supply dissolvent SR-DS play a part of providing reactive hydrogen and usually play a part of main offer reactive hydrogen;
In general, the hydrogen standard state volume of pre-hydrotreating reaction section R10-DD and the volume ratio of coal are less than 300: 1, to reduce short stream
The rate of gasification of journey hydrogen supply dissolvent SR-DS.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, and the gas-liquid separation of at least one intermediate product can be set to walk
Rapid R10-MS sets the liquid stream material coal hydrogenation liquefaction reaction zone of at least two serial operation;
At least part gas-liquid separation step R10-MS discharges contain liquid phase material, into the liquid stream material coal hydrogenation in downstream
Liquefaction reaction zone;
At least part gas-liquid separation step R10-MS discharges contain gaseous phase materials, and the liquid stream material coal for not entering downstream adds
Hydrogen liquefaction reaction zone.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, using liquid stream material coal hydrogenation liquefaction reaction process as base
Standard can inject hydrogen supply dissolvent in batches, i.e., at least using 2 hydrogen-containing hydrocarbon stream addition points, the first hydrogen-containing hydrocarbon stream addition point is
Oily coal refines the starting reaction zone of hydrogenation process R10 altogether, and the second hydrogen-containing hydrocarbon stream addition point is located at the first hydrogen-containing hydrocarbon stream and adds
The downstream of access point.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, using liquid stream material coal hydrogenation liquefaction reaction process as base
Standard, can classify injection hydrogen supply dissolvent, i.e., at least use 2 hydrogen-containing hydrocarbon stream addition points, and mainly higher by normal boiling point
Second hydrogen-containing hydrocarbon stream addition point of hydrocarbon composition is located at the first hydrogen-containing hydrocarbon stream being mainly made of the relatively low hydrocarbon of normal boiling point and adds
The downstream of access point.
The present invention, (3) refine hydrogenation products R10P and are separated into hot gas separated by high pressure separator altogether in thermal high separation process R10P-HS, coal
R10P-HS-V and hot high score oil R10P-HS-L;
In thermal high separation process R10P-HS, air lift hydrogen R10P-HS-BV can be used to contact thermal high separation process
Liquid existing for R10P-HS, with air lift low boiling component therein;In general, gas stripping gas eventually enters into hot gas separated by high pressure separator R10P-HS-V
In.
The present invention, (3) refine hydrogenation products R10P and are separated into hot gas separated by high pressure separator altogether in thermal high separation process R10P-HS, coal
R10P-HS-V and hot high score oil R10P-HS-L;
In general, hot gas separated by high pressure separator R10P-V, hydro carbons therein is mainly made of hydrocarbon of the normal boiling point less than 450 DEG C;
Generally, hot gas separated by high pressure separator R10P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 400 DEG C;
It can be with hot gas separated by high pressure separator R10P-V, hydro carbons therein is mainly made of hydrocarbon of the normal boiling point less than 350 DEG C.
The present invention, (5) separate and recover hot hydrogen-rich gas XH and obtain hydrogen-rich in post processing system R10P-HS-V-AUNIT
Gas XHV and hydrocarbon ils XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles, hydrogen-rich gas hydrogen rich gas
The hydrogen volume concentration of body XHV:Typically larger than 70%, it is generally higher than 80%, preferably greater than 90%;In general, at least part hydrogen-rich
Hydrogenation process is returned after gas XHV purifying hydrogen of hydrogen to recycle.
The present invention, (6) in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L obtains liquefaction production
Object distillate, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C or higher than 530 DEG C;
As needed, a part of liquefied residue VS is used as cycle raffinate VSR to enter oily coal and refines hydrogenation process R10 altogether.
The present invention, (6) in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L obtains liquefaction production
Object distillate, liquefied residue VS;
Partial liquefaction residue VS is recycled back into oil as product VSP, partial liquefaction residue as liquefied residue cycle stock VSR
Coal refines hydrogenation process R10 altogether, for example as liquefied residue cycle stock VSR by coal process for preparation M10 as coal slurry
Configuration solvent naphtha is recycled back into oily coal and refines hydrogenation process R10 altogether.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing,
Can be 1 tunnel or 2 tunnels or multichannel material.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing,
It can be 2 tunnels or multichannel material, hydrogen mode is added using the synchronization of mixed raw material hydrocarbon.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing can
Think 2 hydrogen supply hydrocarbon precursors, the boiling range of 2 hydrogen supply hydrocarbon precursors, molecular structure differ greatly, this 2 road hydrocarbon stream is adopted at this time
Asynchronous add hydrogen mode in following method a kind or several:
1. the first hydrogen supply hydrocarbon precursor mixes latter by hydrogenation products pre- obtained by pre-add hydrogen with the second hydrogen supply hydrocarbon precursor
And add hydrogen;
Products therefrom mixing divides together after 2. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add hydrogen respectively
From;
3. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add after hydrogen after products therefrom mixing together again respectively
Secondary plus hydrogen;
Products therefrom carries out thermal high point respectively after 4. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor add hydrogen respectively
From at least part of each hot high score oil enters oily coal and refines hydrogenation process R10 altogether.
The present invention can comprise the steps of:
(6) it is obtained mainly in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L by routinely boiling
Point is 250~530 DEG C of liquefaction products distillates, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is high
In 500 DEG C;
(7) in solvent oil hydrogenation reaction process R20, under hydrogen, solvent oil hydrogenation catalyst existence condition, before hydrogen supply hydrocarbon
Body object R20F occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into the reaction effluent R20P rich in hydrogen supply hydrocarbon;
Hydrogen supply hydrocarbon precursor R20F, includes at least part distillate oil ML;
In solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 1 tunnel or 2 tunnels or multichannel material.
(8) separation reaction effluent R20P obtains long flow cycle hydrogen supply dissolvent LR-DS;
At least part hydrogen supply dissolvent LR-DS enters oily coal and refines hydrogenation process R10 altogether.
The present invention, (7) in solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 2 tunnels or multichannel material,
The synchronization that mixed raw material hydrocarbon may be used adds hydrogen mode.
The present invention, (7) in solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 2 hydrogen supply hydrocarbon predecessors
Object, the boiling range of 2 hydrogen supply hydrocarbon precursors, molecular structure differ greatly, the asynchronous plus hydrogen mode that this 2 road hydrocarbon stream uses at this time
It can be selected from a kind in following method or several:
1. the first hydrogen supply hydrocarbon precursor mixes latter by hydrogenation products pre- obtained by pre-add hydrogen with the second hydrogen supply hydrocarbon precursor
And add hydrogen;
Products therefrom mixing divides together after 2. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add hydrogen respectively
From;
3. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add after hydrogen after products therefrom mixing together again respectively
Secondary plus hydrogen;
Products therefrom carries out thermal high point respectively after 4. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor add hydrogen respectively
From at least part mixing of each hot high score oil is latter and enters separation/fractionating section LR-DSF.
The present invention, the mode of operation that (2) oil coal refines the reactor that hydrogenation process R10 is used altogether can be in following
1 kind or several of combination:
1. suspension bed, that is, slurry bed system;
2. ebullated bed;
3. slight expanded-bed.
The present invention, the operation of hydrogenation reactor that (4) short route recycled solvent oil hydrogenation modification process R30-UNIT is used
Mode can be selected from a kind or several of combination in following:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion
Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
The present invention, the mode of operation of reactor that (7) solvent oil hydrogenation reaction process R20 is used can be in following
1 kind or several of combination:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion
Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
The present invention, in general, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route cycle solvent
Normal boiling point in oily SR-DS is higher than 250 DEG C of hydro carbons:It is 0.35 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 15%, aromatic carbon rate,
~0.70;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Portion
It is 0.35~0.70 that the weight content of point saturation aromatic hydrocarbons, which is more than 15%, aromatic carbon rate,.
The present invention, generally, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route cycle solvent
Normal boiling point in oily SR-DS is higher than 250 DEG C of hydro carbons:It is 0.40 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,
~0.65;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Portion
It is 0.40~0.65 that the weight content of point saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,.
The present invention, preferably, (4) recycle molten in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route
Normal boiling point in agent oil SR-DS is higher than 250 DEG C of hydro carbons:The weight content of fractional saturation aromatic hydrocarbons is more than 25%, aromatic carbon rate
0.45~0.60;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Portion
It is 0.45~0.60 that the weight content of point saturation aromatic hydrocarbons, which is more than 25%, aromatic carbon rate,.
The present invention, solvent oil hydrogenation reaction process operating condition are usually:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogenation catalyst used is Ni-Mo, Ni-
The hydrogenation catalyst of Co or Ni-W systems;Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is
300~1000NL/kg;
(7) in solvent oil hydrogenation reaction process R20, the hydrogenation catalyst used adds for Ni-Mo, Ni-Co or Ni-W system
Hydrogen catalyst;Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000NL/kg.
The present invention, refining hydrogenation process R10 operating conditions altogether in oily coal is usually:
(2) refine hydrogenation process R10 altogether in oily coal, reaction temperature is 400~465 DEG C, reactor pressure be 6~
30MPa, gas-liquid volume ratio are 600~1500NL/kg, and deliquescence accelerant additive amount is 0.5~3 mass % of dry pulverized coal weight,
Co-catalyst additive amount is that the molar ratio of S/ catalyst activities metal in co-catalyst is 1.0~2.0, and coal slurry solid concentration is 45
~50 mass %.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, the hydrogenation catalyst that can be used, and is a kind of compound
Hydrogenation catalyst includes high-activity component and low activity component;The high-activity component metal and the weight of low activity component metals
Amount is than being 1: 10 to 10: 1;The high-activity component is the water soluble salt compound or its mixture of molybdenum;The low activity group
It is divided into ferric oxide ore or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and catalyst R10C water contents are less than
2wt%;R10C particle diameters are 1~100 μm of powdered granule.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, and direct hydrogenation liquefaction of coal catalyst can surpass for nanometer
Fine grained aqua oxidation iron catalyst and/or iron oxide and/or pyrite and/or bloodstone and/or molybdenum oxide and/or molybdenum sulfide and/or
Ammonium molybdate and/or nickel sulfide.
The present invention in general, (2) refine hydrogenation process R10 altogether in oily coal, uses new hydrogen and/or recycle hydrogen;
(4) in short route recycled solvent oil hydrogenation modification reaction process R30, new hydrogen and/or recycle hydrogen are used;
(7) in solvent oil hydrogenation reaction process R20, new hydrogen and/or recycle hydrogen are used.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 1st kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 2nd kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UN1T, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF prepares solvent and be recycled back into oily coal and refine altogether by coal process for preparation M10 as coal slurry adds hydrogen anti-
Answer process R10.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 3rd kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by coal process for preparation M10 conducts
Coal slurry preparation solvent is recycled back into oily coal and refines hydrogenation process R10 altogether.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 4th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by hydro-upgrading process CR10UNIT
It is converted into the oily coal of hydrogen supply dissolvent oil CSH, CSH return rich in hydrogen supply hydrocarbon and refines hydrogenation process R10 altogether.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 5th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, and richness is converted by hydro-upgrading process
Hydrogen supply dissolvent the oil CSH, CSH of the hydrocarbon containing hydrogen supply prepare solvent as coal slurry by coal process for preparation M10 and are recycled back into oily coal
Refining hydrogenation process R10 altogether.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 6th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the hydro-upgrading process CR10UNIT of depitching distilled oil CFD, CFD that separating step obtains
High-pressure system, stablize the high-pressure system of reaction process R20 with solvent oil hydrogenation, partly or entirely share.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 7th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the hydro-upgrading process CR10UNIT of depitching distilled oil CFD, CFD that separating step obtains
High-pressure system, the high-pressure system with short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, partly or entirely share.
The present invention, (1) are non-coal derived oils, mainly by normal boiling point in coal process for preparation M10, feedstock oil SHVGO
Hydrocarbon composition higher than 530 DEG C.
Description of the drawings
Fig. 1 is the principle process schematic diagram that a kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method, comprising
Coal process for preparation M10, oily coal refine hydrogenation process R10, liquefaction products thermal high separation process R10P-HS, heat height altogether
Divide separation/fractionating section R10P-HS-L-DS, the hot gas separated by high pressure separator R10P-HS-V post processing systems R10P- of oil R10P-HS-L
HS-V-AUNIT, long flow cycle solvent hydrogenation modification reaction process R20, R20 product thermal high separation process R20P-HS, heat
The separation of high score oil R20P-HS-L/fractionating section LR-DSF, liquefaction raffinate fluidisation pyrolysis inverse process BR10UNIT, pyrolytic tar
The hydro-upgrading process CR10UNIT of the distillation process CFDS of CF, the distilled oil CFD of pyrolytic tar CF.
Flow as shown in Figure 1, according to the needs of specific process, some processes or unit can be used or not made
With.
As shown in Figure 1, being total to from conventional oily coal, sweetening process is different, and the present invention is provided with utilizes hot gas separated by high pressure separator R10P-HS-V
In the hydrocarbon component prepare short route cycle solvent hydrogenation modification process R30-UNIT.
As shown in Figure 1, as needed, the precursor hydro carbons R20F of long flow hydrogen supply dissolvent LR-DS may be used, through pipeline
151, which enter solvent oil hydrogenation, stablizes reaction process R20, under hydrogen, long flow solvent oil hydrogenation rugged catalyst existence condition
The reaction of aromatic hydrogenation fractional saturation occurs, is converted into the product R20P rich in hydrogen supply hydrocarbon, separation product R20P is obtained rich in hydrogen supply
The hydrocarbon liquid logistics LS-DS of hydrocarbon, the solvent naphtha that coal is prepared as coal dust SF use.
As shown in Figure 1, as needed, cycle raffinate VSR can be entered coal process for preparation M10 through pipeline 1451, matched
Enter in coal R10F.
As shown in Figure 1, solvent oil hydrogenation reaction product R20P, enters R20P-HS points of thermal high separation process through pipeline 155
From for hot gas separated by high pressure separator R20P-HS-V and hot high score oil R20P-HS-L.
R20P-HS-V includes most of hydrogen, part low boiling hydrocarbon in R20P, and there are many ways of recycling of R20P-HS-V,
It can be the hydrogen-rich gas for being separated into hydrocarbon ils and recycling.
When the pressure of R20P-HS-V, which is higher than oily coal, refines the operating pressure of hydrogenation process R10 altogether, at least part heat
Gas separated by high pressure separator R20P-HS-V can be by secondary use.As shown in Figure 1, enter oily coal through pipeline 165 refines hydrogenation process R10 altogether, than
Such as refine the entrance hydrogen of the first reactor of hydrogenation process R10, the entrance addition hydrogen of rear portion reactor altogether as oily coal,
The hydrogen that cools of hydrogenation process R10 is refined altogether such as oily coal, rinses hydrogen, air lift hydrogen;Delayed heat gas separated by high pressure separator
R20P-HS-V, can be used as hot high score process R10P-HS gas stripping gas use or with the gaseous stream mixed processing based on R10P.
As shown in Figure 1, hot high score oil R20P-HS-L includes part low boiling hydrocarbon in R20P, most of high boiling hydrocarbon, lead to
Often, the hot high score oil R20P-HS-L of at least part isolates long flow and follows through pipeline 166 into separation/fractionating section LR-DSF
Ring hydrogen supply dissolvent LR-DS.
As shown in Figure 1, dispensing coal dust SF enters coal process for preparation M10 through pipeline 101, feedstock oil SHVGO is through pipeline
102 enter coal process for preparation M10, long flow cycle hydrogen supply dissolvent LR-DS enters coal process for preparation through pipeline 175
M10, M10 obtain coal and are used as the raw material R10F that oily coal refines hydrogenation process R10 altogether;As needed, it is prepared in coal
Coal hydrogenation liquefaction catalyst, vulcanizing agent etc. can be incorporated in coal R10F by process M10.
Feedstock oil SHVGO is non-coal derived oils.
As shown in Figure 1, whole coal R10F enters oily coal through pipeline 111 refines hydrogenation process R10 altogether, in hydrogen and
The oily coal that may be used refines hydrogenation catalyst existence condition and issues the swelling of soft coal, be pyrolyzed, be hydrocracked, the coals such as stabilized hydrogenation altogether
Liquefy hydrogenation reaction, while adding hydrogen saturation, adding hydrogen removing impurities matter hydrogenolysis, heat from hydrogenation cracking etc. for raffinate VSR that may be present occurs
Reaction, short cycle hydrogen supply dissolvent SR-DS play hydrogen supply effect, and the dehydrogenation product of hydrogen supply hydrocarbon can be converted into hydrogen supply hydrocarbon weight with repeated hydrogenation
Multiple hydrogen supply plays a part of transmitting reactive hydrogen.
As shown in Figure 1, whole coal R10F enter oily coal refine altogether hydrogenation process R10 be converted into coal hydrogenation liquefaction production
Object R10P, product R10P are separated into hot gas separated by high pressure separator R10P-HS-V and heat through pipeline 121 into thermal high separation process R10P-HS
High score oil R10P-HS-L.
As shown in Figure 1, the R10P-HS-V that pipeline 131 conveys includes most of hydrogen, part low boiling hydrocarbon, heat in R10P
Gas separated by high pressure separator R10P-HS-V recycles hydrogen supply dissolvent hydrogenation modification process R30-UNIT by short route, generates short route cycle hydrogen supply
Solvent SR-DS and hydrogen-rich gas XH.
As shown in Figure 1, hydrogen-rich gas XH enters post processing system R10P-HS-V-AUNIT, separation and recovery through pipeline 341
Hot hydrogen-rich gas XH obtains hydrogen-rich gas hydrogen-rich gas XHV, usually also obtains the hydrocarbon ils XHL discharged through pipeline 196.
Post processing system R10P-HS-V-AUNIT, cooling, water filling washing typically at least including hydrogen-rich gas XH, gas
The processes such as liquid separation or gas and oil water three phase separation, the hydrogen-rich gas and recycling hydrogen-rich gas that the purpose is to obtain to recycle
The operation temperature of hydro carbons in XH, the gas-liquid separation or gas and oil water three phase separation process:Usually 10~80 DEG C, generally
20~70 DEG C, preferably 30~55 DEG C.
It is recycled in general, at least part hydrogen-rich gas XHV returns to hydrogenation process, as shown in Figure 1, a part of hydrogen rich gas
Body hydrogen-rich gas XHV can be returned to oily coal as RH01 by pipeline 195 and refine hydrogenation process R10 recyclings, a part altogether
Hydrogen-rich gas hydrogen-rich gas XHV can return to solvent oil hydrogenation stabilization reaction process R20 cycles as RH02 by pipeline 196 to be made
With,
As shown in Figure 1, new hydrogen FH is conveyed through pipeline 250, FH01 can altogether be refined by pipeline 251 into oily coal all the way plus hydrogen is anti-
Process R10 is answered to be used as the uses such as chemistry consumption hydrogen, FH02 can enter cycle solvent hydrogenation modification reaction process by pipeline 252 all the way
R20 is used as the uses such as chemistry consumption hydrogen.
As shown in Figure 1, hot high score oil R10P-HS-L enters separation/fractionation of hot high score oil R10P-HS-L through pipeline 132
Part R10P-HS-L-DS isolates gas, liquefaction products distillate ML, liquefied residue VS.
In general, partial liquefaction product frac oil ML enters down stream processing steps as product TP1 through pipeline 148, according to need
Will, biology R20F-A enters solvent oil hydrogenation stabilization through pipeline 143 before partial liquefaction product frac oil ML can be used as hydrogen supply agent
Reaction process R20.
As shown in Figure 1, in general, at least part liquefied residue VS enters Downstream processing as product VSP through pipeline 1452
Step plays the role of discharging solid waste, as needed, part liquid as entered liquefaction raffinate fluidisation pyrolysis inverse process BR10UNIT
Coal process for preparation M10, supplying coal R10F can be entered as cycle raffinate VSR through pipeline 1451 by changing residue VS
In.
Oily coal refines the oily coal of hydrogenation process R10 generations and refines hydrogenated oil R10P-O altogether altogether, in general, in hot high score oil
The bottom of towe of vacuum distillation tower that the separate section R10P-HS-L-DS of R10P-HS-L is used obtains mainly by normal boiling point being higher than
VACUUM TOWER BOTTOM material containing solid-liquid VS, that is, raffinate of the present invention of 500~540 DEG C of the hydrocarbon component and solid composition, will can partly subtract
The oily coal of pressure bottom of towe material containing solid-liquid VS returns refines hydrogenation process R10 and is urged as cycle stock VSR with part is used repeatedly altogether
Catalyst particles, deep conversion part heavy hydrocarbon (colloid, asphaltene, preasphaltene), while discharge part VACUUM TOWER BOTTOM contains solid-liquid
Material VS as raffinate product VSP with discharge spent catalyst particles, can not liquefied coal skeleton particle, while carried secretly in raffinate VS
Heavy hydrocarbon such as oil, colloid, asphaltene, preasphaltene, the softening point of raffinate VS is usually above 100~150 DEG C.
The cycle raffinate VSR that oily coal refines hydrogenation process R10 altogether is returned to, because containing can not liquefied dead catalyst
Grain, can not liquefied coal skeleton particle, while carry secretly part heavy hydrocarbon be difficult to plus hydrogen lighting polycyclic aromatic hydrocarbon, glue
Matter, asphaltene, preasphaltene, therefore the presence of cycle stock VSR, although can recovery section oil product, be significantly degrading oil
Coal refines the operating condition of hydrogenation process R10 and its related system altogether, shortens the continuous operation period, limits or has compressed original
Material coal range (mainly proposes the content of ashes and inertinite content of fine coal upper limit requirement).
As shown in Figure 1, the present invention forms oily coal and refines short circuit currents of the hydrogenation process R10 with light solvent oil altogether
Journey.
As shown in Figure 1, as needed, solvent oil hydrogenation can be set to stablize reaction process R20, can be processed from pipeline
143 distillate R20F-A can process the suitable fraction of boiling range conveyed through pipeline 196 of R10P-HS-V-AUNIT discharges
The oily R20F-B warm high score oil that such as warm high score separation process obtains, can also process other suitable distillates.
Solvent oil hydrogenation stablizes reaction process R20, can process 2 or multiple hydrogen supply hydrocarbon precursors, mixing may be used
The synchronization of raw material hydrocarbon adds hydrogen mode.
Solvent oil hydrogenation stablizes reaction process R20, and the boiling range of 2 hydrogen supply hydrocarbon precursors of processing, molecular structure may
When differing greatly, nonsynchronous plus hydrogen mode may be used in this 2 road hydrocarbon stream, for example can be that distillate R20F-A passes through pre-add
Add hydrogen after pre- hydrogenation products are mixed with distillate R20F-B obtained by hydrogen together;For example can be that distillate R20F-B passes through pre-add hydrogen
The pre- hydrogenation products of gained add hydrogen together after being mixed with distillate R20F-A;For example can be distillate R20F-A, distillate R20F-
Products therefrom mixing detaches together after B parallel connections add hydrogen respectively;For example can be distillate R20F-A, distillate R20F-B parallel connections point
Plus after hydrogen hydrogen is not added again after products therefrom mixing together;For example can be that distillate R20F-A, distillate R20F-B add respectively
Products therefrom carries out thermal high separation respectively after hydrogen, and at least part of each hot gas separated by high pressure separator enters oily coal and refines hydrogenation reaction mistake altogether
Journey R10.
As shown in Figure 1, solvent oil hydrogenation stablizes reaction process R20, can process 2 or multiple hydrogen supply hydrocarbon precursors,
It is carried out in a set of high-pressure system, therefore investment is smaller, energy consumption is relatively low.
As shown in Figure 1, the present invention is molten there is provided short route cycle is prepared using the hydrocarbon component in hot gas separated by high pressure separator R10P-HS-V
Agent hydrogenation modification process R30-UNIT, overall goal are:
1. prepare short route cycle hydrogen supply dissolvent SR-DS using the hydrocarbon component in hot gas separated by high pressure separator R10P-HS-V;
2. it recycles in hot gas separated by high pressure separator R10P-HS-V and does not enter into short route cycle solvent hydrogenation modification process R30-
UNIT or the components such as hydrogen for not entering into short route cycle solvent, these components form logistics XH after the entrance of pipeline 341
Put processing system R10P-HS-V-AUNIT.
As shown in Figure 1, recycling solvent hydrogenation modification process R30-UNIT in short route, as needed, can use through pipe
The such as new hydrogen of raw material XF or recycle hydrogen logistics or gas hydrogen that road 315 conveys, may production according to the needs of practical flow scheme
The raw product X P such as hydrogens conveyed through pipeline 320 and/or hydrocarbonaceous product.
Fig. 2 is the hot gas separated by high pressure separator R10P-HS-V of use that a kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method
Middle hydrocarbon ils prepares the principle process schematic diagram of the 1st kind of technical solution of the R30-UNIT of short route hydrogen supply hydrocarbon, is hot gas separated by high pressure separator
R10P-HS-V is directly entered the online stabilized hydrogenation method of postposition of reaction process R30, and solvent is recycled comprising short route is prepared
Thermal high separation process R30P-HS, the delivery pump A-PUMP of hydrogenation modification reaction process R30, R30 product R30P.
As shown in Fig. 2, the precursor of short route hydrogen supply dissolvent SR-DS is the hydro carbons in hot gas separated by high pressure separator R10P-HS-V, heat is high
Gas R10P-HS-V is divided to enter short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30 through pipeline 131, is supplied in hydrogen, short route
The reaction of aromatic hydrogenation fractional saturation occurs under hydrogen solvent oil hydrogenation rugged catalyst existence condition, is converted into the production rich in hydrogen supply hydrocarbon
Object R30P, separation product R30P obtain the hydrocarbon liquid logistics SR-DS rich in hydrogen supply hydrocarbon, and hydrogenation process R10 is refined altogether into oily coal.
As shown in Fig. 2, product R30P is separated into hot gas separated by high pressure separator through pipeline 311 into thermal high separation process R30P-HS
R30P-HS-V and hot high score oil R30P-HS-L, hot gas separated by high pressure separator R30P-HS-V are used as logistics XH, hot high score oil R30P-HS-
L is used as logistics SR-DS.
As shown in Fig. 2, thermal high separation process R30P-HS, the purpose is to obtain hydrogen supply hydrocarbon and isolate other component groups
Into gas, any appropriate operating condition can be used.Usual hot high score oil R30P-HS-L is mainly higher than 280 by normal boiling point
DEG C or higher than 230 DEG C hydro carbons composition, the operation temperature of the gas-liquid separation process:Usually 150~330 DEG C, it is general
It is 180~280 DEG C, preferably 200~250 DEG C.
As shown in Fig. 2, hot gas separated by high pressure separator R10P-HS-V has been directly entered reaction process R30, and therefore, hot high score oil R30P-
The operating pressure of HS-L is less than the operating pressure that oily coal refines hydrogenation process R10 altogether, and hot high score oil R30P-HS-L is through pipeline
After 351 enter pump A-PUMP pressurizations, enter oily coal through pipeline 352 and refine hydrogenation process R10 altogether as logistics SR-DS.
As shown in Fig. 2, as needed, thermal high separation process R30P-HS can use the air lift conveyed through pipeline 3158
Liquid existing for hydrogen R30P-HS-BV contact thermal high separation processes R30P-HS, with air lift low boiling component therein, air lift
Gas may finally be entered in hot gas separated by high pressure separator R30P-HS-V.
About scheme shown in Fig. 2, advantage is reuse hydrogen and flow is simple, the drawback is that not being avoided that hot high score
The foreign gas of gas R10P-HS-V such as H2O、NH3、CO、CO2, HCL introducing R30, these foreign gas severe exacerbations R30 urges
Agent operation efficiency (cause R30 catalyst lifes are short, hydrogen supply dissolvent quality is unstable).
The shortcomings that in order to overcome scheme shown in Fig. 2, it is proposed that the temperature of the hot gas separated by high pressure separator R10P-HS-V of setting shown in Fig. 3 is high
The flow of separation process R10P-HS-V-MS is pressed, hot gas separated by high pressure separator R10P-HS-V is at warm high pressure separation process R10P-HS-V-MS points
Enter from for warm gas separated by high pressure separator R10P-HS-V-MS-V and temperature high score oil R10P-HS-V-MS-L, warm high score oil R10P-HS-V-MS-L
Short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30.
Fig. 3 is the hot gas separated by high pressure separator R10P-HS-V of use that a kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method
Middle hydrocarbon ils prepares the principle process schematic diagram of the 2nd kind of technical solution of short route hydrogen supply hydrocarbon part R30-UNIT, with side shown in Fig. 2
Case is compared, and increases the warm high pressure separation process R10P-HS-V-MS of hot gas separated by high pressure separator R10P-HS-V, is warm high score oil R10P-HS-
V-MS-L enters the online stabilized hydrogenation method of postposition of short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, includes temperature
High pressure separation process R10P-HS-V-MS, hydrogenation modification reaction process R30, the R30 product R30P for preparing short route cycle solvent
Thermal high separation process R30P-HS, delivery pump A-PUMP.
As shown in figure 3, hot gas separated by high pressure separator R10P-HS-V enters warm high pressure separation process R10P-HS-V-MS through pipeline 131, point
From for warm gas separated by high pressure separator R10P-HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, warm high score oil R10P-HS-V-MS-L is through pipe
Road 305 is used into short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, hot gas separated by high pressure separator R30P-HS-V as logistics XH.
As shown in figure 3, as needed, warm high pressure separation process R10P-HS-V-MS can be used and be conveyed through pipeline 3151
The warm high pressure separation process R10P-HS-V-MS of air lift hydrogen R10P-HS-V-MS-BV contacts existing for liquid, with air lift wherein
Low boiling component, gas stripping gas may finally be entered in warm gas separated by high pressure separator R10P-HS-V-MS-V.
As shown in figure 3, warm high pressure separation process R10P-HS-V-MS, the purpose is to obtain hydrogen supply hydrocarbon precursor and isolate
The gas of other component compositions, can be used any appropriate operating condition.Usually temperature high score oil R10P-HS-V-MS-L mainly by
Hydro carbons composition of the normal boiling point higher than 250 DEG C or higher than 200 DEG C, the gas of the warm high pressure separation process R10P-HS-V-MS
The operation temperature of liquid separation process:Usually 150~330 DEG C, generally 180~280 DEG C, preferably 200~250 DEG C.
About scheme shown in Fig. 3, advantage is that of avoiding the foreign gas such as H of hot gas separated by high pressure separator R10P-HS-V2O、NH3、CO、
CO2, HCL enter reaction process R30, the drawback is that hydrogen can not be reused, therefore air system flow is complicated, investment is big.
The shortcomings that in order to overcome scheme shown in Fig. 3, it is proposed that scheme shown in Fig. 4, Fig. 5 is setting hot gas separated by high pressure separator R10P-
Under the premise of the warm high pressure separation process R10P-HS-V-MS of HS-V, by the booster pump on the circulation route of short route hydrogen supply dissolvent
Position is adjusted to the booster pump of warm high score oil R10P-HS-V-MS-L, can improve reaction process R30, R30 product R30P in this way
The operating pressure of thermal high separation process R30P-HS make it higher than the operating pressure that oily coal refines hydrogenation process R10 altogether, be
The hot high score gas-liquid logistics of R30P or R30P relies on and refines hydrogenation process R10 altogether into oily coal and create conditions from being pressed into, anti-in this way
The hydrogen in product R30P is answered secondary be pressed into certainly using such as dependence can to refine hydrogenation process altogether into oily coal as needed
R10。
Fig. 4 is the hot gas separated by high pressure separator R10P-HS-V of use that a kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method
Middle hydrocarbon ils prepares the principle process schematic diagram of the 3rd kind of technical solution of short route hydrogen supply hydrocarbon part R30-UNIT, with side shown in Fig. 3
Case is compared, and is cancelled the booster pump A-PUMP of short route hydrogen supply dissolvent in flow, is increased warm high score oil R10P-HS-V-MS-
LB-PUNP booster pumps improve the operating pressure of the thermal high separation process R30P-HS of reaction process R30, R30 product R30P,
The operating pressure that oily coal refines hydrogenation process R10 altogether is made it higher than, forms the online stabilized hydrogenation method of forward type;Setting temperature
High pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, the hydrogenation modification reaction process for preparing short route cycle solvent
The thermal high separation process R30P-HS of R30, R30 product R30P, comprise the steps of:
As shown in figure 4, hot gas separated by high pressure separator R10P-HS-V enters warm high pressure separation process R10P-HS-V-MS through pipeline 131, point
From for warm gas separated by high pressure separator R10P-HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, warm high score oil R10P-HS-V-MS-L is through pipe
Road 305 is used into short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, hot gas separated by high pressure separator R30P-HS-V as logistics XH.
As shown in figure 4, as needed, warm high pressure separation process R10P-HS-V-MS can be used and be conveyed through pipeline 3151
The warm high pressure separation process R10P-HS-V-MS of air lift hydrogen R10P-HS-V-MS-BV contacts existing for liquid, with air lift wherein
Low boiling component, gas stripping gas may finally be entered in warm gas separated by high pressure separator R10P-HS-V-MS-V.
As shown in figure 4, temperature high score oil R10P-HS-V-MS-L through pipeline 305 enter pump B-PUMP pressurization after, through pipeline 307
Into short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30.
As shown in figure 4, the precursor R30F of short route hydrogen supply dissolvent SR-DS, that is, temperature after supercharged high score oil R10P-HS-V-
MS-L enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30 through pipeline 307, in hydrogen, short route hydrogen supply dissolvent oil
The reaction of aromatic hydrogenation fractional saturation occurs under stabilized hydrogenation catalyst existence condition, is converted into the product R30P rich in hydrogen supply hydrocarbon.
As shown in figure 4, product R30P is separated into hot gas separated by high pressure separator through pipeline 311 into thermal high separation process R30P-HS
R30P-HS-V and hot high score oil R30P-HS-L, hot high score oil R30P-HS-L are used as logistics SR-DS.
As shown in figure 4, thermal high separation process R30P-HS, the purpose is to obtain hydrogen supply hydrocarbon and isolate other component groups
Into gas, any appropriate operating condition can be used.Usual hot high score oil R30P-HS-L is mainly higher than 280 by normal boiling point
DEG C or higher than 230 DEG C hydro carbons composition, the operation temperature of the gas-liquid separation process:Usually 150~330 DEG C, it is general
It is 180~280 DEG C, preferably 200~250 DEG C.
As shown in figure 4, temperature gas separated by high pressure separator R10P-HS-V-MS-V enters post processing system R10P-HS-V- through pipeline 301
AUNIT。
As shown in figure 4, hot gas separated by high pressure separator R30P-HS-V is conveyed through pipeline 341, oily coal can be entered and refine hydrogenation process altogether
R10's needs position.
About scheme shown in Fig. 4, advantage is that of avoiding the foreign gas such as H of hot gas separated by high pressure separator R10P-HS-V2O、NH3、CO、
CO2, HCL enter R30, hydrogen may be reused and flow is simple, and the secondary use of hydrogen can be that multipaths point is more
As uses such as new hydrogen, quenching hydrogen, flushing hydrogen, air lift hydrogen, the use of short route hydrogen supply dissolvent oil can be multipaths point at place
Many places are as the uses such as hydrogen supply agent, flushing oil, cooling oil, flexibility bigger.
Fig. 5 is the hot gas separated by high pressure separator R10P-HS-V of use that a kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method
Middle hydrocarbon ils prepares the principle process schematic diagram of the 4th kind of technical solution of short route hydrogen supply hydrocarbon part R30-UNIT, with side shown in Fig. 4
Case is compared, and eliminates hydrogen supply hydrocarbon in thermal high separation process R30P-HS, the R30 product R30P of R30 products R30P, hydrogen
The position that needs that oily coal refines hydrogenation process R10 altogether is entered together Deng whole components, such as starting reaction compartment, intermediate anti-
Answer space, final reaction space.
A kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total in smelting method, hydrocarbon ils in hot gas separated by high pressure separator R10P-HS-V
Prepare short route hydrogen supply hydrocarbon prepare part R30 and/or short recycled solvent oil cycle approach technical solution also there are many, do not have
It represents in the accompanying drawings, such as:
1. classification injection hydrogen supply dissolvent SR-DS refines the different location of hydrogenation process R10 to oily coal altogether in batches;It will at least
A part of short route hydrogen supply hydrocarbon SR-DS introduces the intermediate reaction area or final reaction zone that oily coal refines hydrogenation process R10 altogether, will
At least part higher boiling hydrogen supply hydrocarbon introduces the intermediate reaction area or final reaction zone that oily coal refines hydrogenation process R10 altogether;
2. oily coal refines hydrogenation process R10 altogether to be made to include 2 or multiple order of reactions, gas-liquid separation step is used between grade,
At least part separation liquid is introduced into next stage reaction zone or cycle plus hydrogen, at least part separation gas is drawn into reaction system
Without entering next stage reaction zone;Each order of reaction needs to add in new hydrogen material;
3. oily coal refines hydrogenation process R10 altogether, chilling logistics such as chilling hydrogen and/or quench oil are used;
4. thermal high separation process R10P-HS using gas hydrogen, reduces the low boiling point in hot high score oil R10P-HS-L
Constituent content;
5. higher boiling hydrogen supply hydrocarbon hydrocarbon prepares the high-pressure hydrogenation system of part R20, prepare part R30's with short route hydrogen supply hydrocarbon
High-pressure hydrogenation system, partial common.
Specific embodiment
The present invention described in detail below.
Pressure of the present invention, refers to absolute pressure.
Normal boiling point of the present invention refers to vapour of the substance under an atmospheric pressure, liquid equilibrium temperature.
Routine boiling range of the present invention refers to the normal boiling point range of fraction.
Proportion of the present invention, unless stated otherwise, refer to normal pressure, fluid density and normal pressure under the conditions of 15.6 DEG C,
The ratio of water density under the conditions of 15.6 DEG C.
The composition or concentration or content or yield value of component of the present invention are weight basis unless stated otherwise
Value.
Conventional gas hydrocarbon of the present invention is referred in gaseous hydro carbons under normal condition, including methane, ethane, third
Alkane, butane.
Conventional liq hydrocarbon of the present invention, refers to the hydro carbons being in a liquid state under normal condition, including pentane and its boiling point
Higher hydro carbons.
Impurity element of the present invention, refer to non-hydrogen in feedstock oil, non-carbon, nonmetallic ingredient for example oxygen, sulphur, nitrogen,
Chlorine etc..
Impurity composition of the present invention refers to hydro-conversion object such as water, ammonia, the vulcanization of non-hydrocarbon component in feedstock oil
Hydrogen, hydrogen chloride etc..
Light hydrocarbon of the present invention is naphtha component, refers to that normal boiling point is less than 200 DEG C of conventional liq hydrocarbon.
Middle matter hydrocarbon of the present invention is diesel component, refers to the hydro carbons that normal boiling point is 200~330 DEG C.
Wax oil component of the present invention refers to the hydro carbons that normal boiling point is 330~530 DEG C.
Heavy hydrocarbon of the present invention refers to that normal boiling point is higher than 330 DEG C of hydro carbons.
Hydrogen to oil volume ratio of the present invention refers to the standard state volume flow of hydrogen with specifying the normal of oily logistics
The ratio of pressure, 20 DEG C of volume flow.
Polycyclic aromatic hydrocarbon mentioned herein, aromatic ring number >=3.
Up flow type hydrogenation reactor of the present invention, reaction compartment or the processing medium in hydrogenation catalyst bed
Macroscopic view flowing dominant direction is from top to bottom.
The present invention is described in detail below in conjunction with attached drawing, attached drawing is drawn to describe the present invention, but it cannot be limited
The application range of the fixed present invention.
Up flow type expanded bed hydrogenation reactor of the present invention, the basic element of character usually have:
1. reactor shell;
2. the opening (or to take over) in reactor shell;
3. the up flow type being arranged in reactor enclosure body adds hydrogen main reaction space, usually using catalyst during working condition,
It is used to be uniformly distributed charging usually using charging distributed component;
4. it is arranged in the feed distributor of bottom in reactor enclosure body;
5. it is arranged in epimere or the liquid collection cups LD of middle epimere and liquid conduits LK in reactor enclosure body;
6. reactor intermediate feed distributor (or distributor), such as mixer of catalyst bed interlayer, cold hydrogen box;
7. rectification part is exported, such as collector, liquid phase discharge vortex-proof device, mixed phase product fairlead.
8. the measuring instrumentss that may be installed:The temperature-measuring part such as thermocouple of reaction bed temperature is tested, measures reactor
The pressure gauge of system specific location pressure measures liquid level instrument such as glass plate, floating drum, double flange difference gauges, the guided wave of liquid level
Radar, ray level-sensing device etc.;
Up-flow reactor of the present invention, accessory is external insulation material, support element (skirt or journal stirrup), base
Plinth, ladder, operating platform and fire-fighting accessory that may be present such as steam smothering ring.According to the conditions such as ground geology, meteorology are built, tie
The conditions such as weight of equipment, height are closed, up-flow reactor of the present invention needs piling to control under its basis as needed
The sinking speed on its basis.
Oil coal of the invention refines hydrogenation process R10 altogether, and usually using up-flow reactor, working method can select:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion
Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve;
3. slight expanded-bed.
Solvent oil hydrogenation of the present invention stablizes reaction process R20, R30, the reactor used, and working method can select:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion
Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
Suspended-bed reactor of the present invention, structure type can be any one suitable forms, can be empty cylinder
Suspended-bed reactor can be so as to shape using internal cycle guide shell so as to form piston flow or the back-mixing stream there are interior cycle
Circulation or internal outside circulation in into inside can top reaction compartment liquid be made to flow into lower part reaction sky using its outer circulating tube
Between shaper outer circulation stream back-mixing flow pattern, can be using top product liquid collect and flow guide system so as to by cycle plus
Pressure system forms the back-mixing flow pattern for forcing inner recirculation flow.
The characteristic of the present invention is described below.
A kind of oily coal with short cycle hydrogen supply dissolvent oil of the present invention is total to smelting method, it is characterised in that comprises the steps of:
(1) it is made into coal R10F in coal process for preparation M10, feedstock oil SHVGO, the coal dust SF of non-coal derived oils;
(2) hydrogenation process R10 is refined altogether in oily coal, in short route recycled solvent oil SR-DS, hydrogen from step (4)
Gas, the oily coal that may be used are refined altogether under hydrogenation catalyst existence condition, and coal R10F is converted into coal and refines hydrogenation products R10P altogether;
Hydrogenation process R10 is refined altogether in oily coal, and the coal dust in coal R10F occurs the swelling of coal, pyrolysis, hydrogen added to split
The lightings such as thermal cracking, stabilized hydrogenation occur for the Coal liquefactions such as change, stabilized hydrogenation, the feedstock oil SHVGO in coal R10F
Reaction, short route recycled solvent oil SR-DS is at least to the effect of pyrolysis free radical release reactive hydrogen;
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V altogether
With hot high score oil R10P-HS-L;
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in short route recycled solvent oil hydrogenation modification
Reaction process R30 under hydrogen, short route recycled solvent oil hydrogenation catalyst existence condition, includes hot gas separated by high pressure separator R10P-HS-V
The hydrogen supply hydrocarbon precursor R30F of middle the hydrocarbon component occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into rich in hydrogen supply hydrocarbon
Reaction effluent R30P;
High pressure stream comprising the hydrocarbon component in reaction effluent R30P is used as short route recycled solvent oil SR-DS, into
Enter oily coal and refine hydrogenation process R10 altogether;
It is used as hydrogen-rich stream XH comprising the high pressure gas logistics for carrying out hydrogen in self-heating gas separated by high pressure separator R10P-HS-V;
(5) in post processing system R10P-HS-V-AUNIT, separation and recovery hydrogen-rich gas XH obtain hydrogen-rich gas XHV and
Hydrocarbon ils XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles.
The present invention, the 1st kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is that postposition is online plus hydrogen changes
Property method, hot gas separated by high pressure separator R10P-HS-V is directly entered reaction process R30, and setting short route recycles the hydrogenation modification reaction of solvent
Thermal high separation process R30P-HS, the delivery pump A-PUMP of process R30, R30 product R30P, comprises the steps of:
1. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, add hydrogen steady in hydrogen, short route hydrogen supply dissolvent oil
Determining under catalyst existence condition, hot gas separated by high pressure separator R10P-HS-V enters reaction process R30 and switchs to the product R30P rich in hydrogen supply hydrocarbon,
The reaction of at least part aromatic hydrogenation fractional saturation occurs for the hydrocarbon component that hot gas separated by high pressure separator R10P-HS-V is carried;
2. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH, the hot high score oil R30P-HS-L warps of at least part
Enter oily coal as logistics SR-DS after delivery pump A-PUMP pressurizations and refine hydrogenation process R10 altogether.
The present invention, the 2nd kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is that postposition is online plus hydrogen changes
Property method, hot gas separated by high pressure separator R10P-HS-V is in warm high score oil R10P- isolated warm high pressure separation process R10P-HS-V-MS
HS-V-MS-L enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, sets warm high pressure separation process R10P-HS-V-
MS, the thermal high separation process R30P- that short route recycles hydrogenation modification reaction process R30, the R30 product R30P of solvent is prepared
HS, delivery pump A-PUMP, comprise the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L;
Hot gas separated by high pressure separator R30P-HS-V is used as logistics XH at least partially;
2. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, add hydrogen steady in hydrogen, short route hydrogen supply dissolvent oil
Determine under catalyst existence condition, warm high score oil R10P-HS-V-MS-L enters reaction process R30 and is converted into the production rich in hydrogen supply hydrocarbon
The reaction of at least part aromatic hydrogenation fractional saturation occurs for object R30P, the hydrocarbon component that hot gas separated by high pressure separator R10P-HS-V is carried;
3. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH, the hot high score oil R30P-HS-L warps of at least part
Enter oily coal as logistics SR-DS after delivery pump A-PUMP pressurizations and refine hydrogenation process R10 altogether.
The present invention, the 3rd kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model changes for preposition online plus hydrogen
Property method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent plus hydrogen change
The thermal high separation process R30P-HS of property reaction process R30, R30 product R30P, comprises the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the predecessor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of object R30F, in hydrogen, there are items for short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst
The reaction of at least part aromatic hydrogenation fractional saturation occurs under part, is converted into the product R30P rich in hydrogen supply hydrocarbon;
4. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot high score oil R30P-HS-L of at least part enter oily coal as logistics SR-DS and refine hydrogenation process altogether
R10。
The present invention, the 4th kind of flow model of short route recycled solvent oil hydrogenation modification process R30-UNIT are:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model changes for preposition online plus hydrogen
Property method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent plus hydrogen change
The thermal high separation process R30P-HS of property reaction process R30, R30 product R30P, comprises the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the predecessor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of object R30F, in hydrogen, there are items for short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst
The reaction of at least part aromatic hydrogenation fractional saturation occurs under part, is converted into the product R30P rich in hydrogen supply hydrocarbon, at least part
Hot high score oil R30P-HS-L enters oily coal as logistics SR-DS and refines hydrogenation process R10 altogether.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process
R30P-HS can use liquid existing for air lift hydrogen R30P-HS-BV contact thermal high separation processes R30P-HS, with air lift
Low boiling component therein, gas stripping gas enter in hot gas separated by high pressure separator R30P-HS-V.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process
R30P-HS, hot high score oil R30P-HS-L are mainly made of hydro carbons of the normal boiling point higher than 280 DEG C or higher than 230 DEG C.
The present invention, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, thermal high separation process R30P-
The operation temperature of HS:Usually 150~330 DEG C, generally 180~280 DEG C, preferably 200~250 DEG C.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in warm high pressure separation process
R10P-HS-V-MS can use air lift hydrogen R10P-HS-V-MS-BV contacts temperature high pressure separation process R10P-HS-V-MS to deposit
Liquid, with air lift low boiling component therein, gas stripping gas may finally be entered in warm gas separated by high pressure separator R10P-HS-V-MS-V.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in warm high pressure separation process
R10P-HS-V-MS, warm high score oil R10P-HS-V-MS-L are mainly by hydro carbons group of the normal boiling point higher than 250 DEG C or higher than 200 DEG C
Into.
The present invention, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, warm high pressure separation process R10P-
The operation temperature of HS-V-MS:Usually 150~330 DEG C, generally 180~280 DEG C, preferably 200~250 DEG C.
The present invention, (1) quality of pc concentration in coal process for preparation M10, coal slurry R10F:Typically larger than 30%, one
As be more than 40%, more preferably greater than 45%.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, can set pre-hydrotreating reaction section R10-DD;
In pre-hydrotreating reaction section R10-DD, coal R10F occurs pre-hydrotreating reaction and is converted into the pre- hydrogenation products R10- of coal
DD-P, short route hydrogen supply dissolvent SR-DS play a part of providing reactive hydrogen and usually play a part of main offer reactive hydrogen;
In general, the hydrogen standard state volume of pre-hydrotreating reaction section R10-DD and the volume ratio of coal are less than 300: 1, to reduce short stream
The rate of gasification of journey hydrogen supply dissolvent SR-DS.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, and the gas-liquid separation of at least one intermediate product can be set to walk
Rapid R10-MS sets the liquid stream material coal hydrogenation liquefaction reaction zone of at least two serial operation;
At least part gas-liquid separation step R10-MS discharges contain liquid phase material, into the liquid stream material coal hydrogenation in downstream
Liquefaction reaction zone;
At least part gas-liquid separation step R10-MS discharges contain gaseous phase materials, and the liquid stream material coal for not entering downstream adds
Hydrogen liquefaction reaction zone.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, using liquid stream material coal hydrogenation liquefaction reaction process as base
Standard can inject hydrogen supply dissolvent in batches, i.e., at least using 2 hydrogen-containing hydrocarbon stream addition points, the first hydrogen-containing hydrocarbon stream addition point is
Oily coal refines the starting reaction zone of hydrogenation process R10 altogether, and the second hydrogen-containing hydrocarbon stream addition point is located at the first hydrogen-containing hydrocarbon stream and adds
The downstream of access point.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, using liquid stream material coal hydrogenation liquefaction reaction process as base
Standard, can classify injection hydrogen supply dissolvent, i.e., at least use 2 hydrogen-containing hydrocarbon stream addition points, and mainly higher by normal boiling point
Second hydrogen-containing hydrocarbon stream addition point of hydrocarbon composition is located at the first hydrogen-containing hydrocarbon stream being mainly made of the relatively low hydrocarbon of normal boiling point and adds
The downstream of access point.
The present invention, (3) refine hydrogenation products R10P and are separated into hot gas separated by high pressure separator altogether in thermal high separation process R10P-HS, coal
R10P-HS-V and hot high score oil R10P-HS-L;
In thermal high separation process R10P-HS, air lift hydrogen R10P-HS-BV can be used to contact thermal high separation process
Liquid existing for R10P-HS, with air lift low boiling component therein;In general, gas stripping gas eventually enters into hot gas separated by high pressure separator R10P-HS-V
In.
The present invention, (3) refine hydrogenation products R10P and are separated into hot gas separated by high pressure separator altogether in thermal high separation process R10P-HS, coal
R10P-HS-V and hot high score oil R10P-HS-L;
In general, hot gas separated by high pressure separator R10P-V, hydro carbons therein is mainly made of hydrocarbon of the normal boiling point less than 450 DEG C;
Generally, hot gas separated by high pressure separator R10P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 400 DEG C;
It can be with hot gas separated by high pressure separator R10P-V, hydro carbons therein is mainly made of hydrocarbon of the normal boiling point less than 350 DEG C.
The present invention, (5) separate and recover hot hydrogen-rich gas XH and obtain hydrogen-rich in post processing system R10P-HS-V-AUNIT
Gas XHV and hydrocarbon ils XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles, hydrogen-rich gas hydrogen rich gas
The hydrogen volume concentration of body XHV:Typically larger than 70%, it is generally higher than 80%, preferably greater than 90%;In general, at least part hydrogen-rich
Hydrogenation process is returned after gas XHV purifying hydrogen of hydrogen to recycle.
The present invention, (6) in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L obtains liquefaction production
Object distillate, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C or higher than 530 DEG C;
As needed, a part of liquefied residue VS is used as cycle raffinate VSR to enter oily coal and refines hydrogenation process R10 altogether.
The present invention, (6) in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L obtains liquefaction production
Object distillate, liquefied residue VS;
Partial liquefaction residue VS is recycled back into oil as product VSP, partial liquefaction residue as liquefied residue cycle stock VSR
Coal refines hydrogenation process R10 altogether, for example as liquefied residue cycle stock VSR by coal process for preparation M10 as coal slurry
Configuration solvent naphtha is recycled back into oily coal and refines hydrogenation process R10 altogether.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing,
Can be 1 tunnel or 2 tunnels or multichannel material.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing,
It can be 2 tunnels or multichannel material, hydrogen mode is added using the synchronization of mixed raw material hydrocarbon.
The present invention, (4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing can
Think 2 hydrogen supply hydrocarbon precursors, the boiling range of 2 hydrogen supply hydrocarbon precursors, molecular structure differ greatly, this 2 road hydrocarbon stream is adopted at this time
Asynchronous add hydrogen mode in following method a kind or several:
1. the first hydrogen supply hydrocarbon precursor mixes latter by hydrogenation products pre- obtained by pre-add hydrogen with the second hydrogen supply hydrocarbon precursor
And add hydrogen;
Products therefrom mixing divides together after 2. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add hydrogen respectively
From;
3. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add after hydrogen after products therefrom mixing together again respectively
Secondary plus hydrogen;
Products therefrom carries out thermal high point respectively after 4. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor add hydrogen respectively
From at least part of each hot high score oil enters oily coal and refines hydrogenation process R10 altogether.
The present invention can comprise the steps of:
(6) it is obtained mainly in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L by routinely boiling
Point is 250~530 DEG C of liquefaction products distillates, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is high
In 500 DEG C;
(7) in solvent oil hydrogenation reaction process R20, under hydrogen, solvent oil hydrogenation catalyst existence condition, before hydrogen supply hydrocarbon
Body object R20F occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into the reaction effluent R20P rich in hydrogen supply hydrocarbon;
Hydrogen supply hydrocarbon precursor R20F, includes at least part distillate oil ML;
In solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 1 tunnel or 2 tunnels or multichannel material.
(8) separation reaction effluent R20P obtains long flow cycle hydrogen supply dissolvent LR-DS;
At least part hydrogen supply dissolvent LR-DS enters oily coal and refines hydrogenation process R10 altogether.
The present invention, (7) in solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 2 tunnels or multichannel material,
The synchronization that mixed raw material hydrocarbon may be used adds hydrogen mode.
The present invention, (7) in solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 2 hydrogen supply hydrocarbon predecessors
Object, the boiling range of 2 hydrogen supply hydrocarbon precursors, molecular structure differ greatly, the asynchronous plus hydrogen mode that this 2 road hydrocarbon stream uses at this time
It can be selected from a kind in following method or several:
1. the first hydrogen supply hydrocarbon precursor mixes latter by hydrogenation products pre- obtained by pre-add hydrogen with the second hydrogen supply hydrocarbon precursor
And add hydrogen;
Products therefrom mixing divides together after 2. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add hydrogen respectively
From;
3. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add after hydrogen after products therefrom mixing together again respectively
Secondary plus hydrogen;
Products therefrom carries out thermal high point respectively after 4. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor add hydrogen respectively
From at least part mixing of each hot high score oil is latter and enters separation/fractionating section LR-DSF.
The present invention, the mode of operation that (2) oil coal refines the reactor that hydrogenation process R10 is used altogether can be in following
1 kind or several of combination:
1. suspension bed, that is, slurry bed system;
2. ebullated bed;
3. slight expanded-bed.
The present invention, the operation of hydrogenation reactor that (4) short route recycled solvent oil hydrogenation modification process R30-UNIT is used
Mode can be selected from a kind or several of combination in following:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion
Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
The present invention, the mode of operation of reactor that (7) solvent oil hydrogenation reaction process R20 is used can be in following
1 kind or several of combination:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion
Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
The present invention, in general, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route cycle solvent
Normal boiling point in oily SR-DS is higher than 250 DEG C of hydro carbons:It is 0.35 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 15%, aromatic carbon rate,
~0.70;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Portion
It is 0.35~0.70 that the weight content of point saturation aromatic hydrocarbons, which is more than 15%, aromatic carbon rate,.
The present invention, generally, (4) are in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route cycle solvent
Normal boiling point in oily SR-DS is higher than 250 DEG C of hydro carbons:It is 0.40 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,
~0.65;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Portion
It is 0.40~0.65 that the weight content of point saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,.
The present invention, preferably, (4) recycle molten in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route
Normal boiling point in agent oil SR-DS is higher than 250 DEG C of hydro carbons:The weight content of fractional saturation aromatic hydrocarbons is more than 25%, aromatic carbon rate
0.45~0.60;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Portion
It is 0.45~0.60 that the weight content of point saturation aromatic hydrocarbons, which is more than 25%, aromatic carbon rate,.
The present invention, solvent oil hydrogenation reaction process operating condition are usually:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogenation catalyst used is Ni-Mo, Ni-
The hydrogenation catalyst of Co or Ni-W systems;Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is
300~1000NL/kg;
(7) in solvent oil hydrogenation reaction process R20, the hydrogenation catalyst used adds for Ni-Mo, Ni-Co or Ni-W system
Hydrogen catalyst;Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000NL/kg.
The present invention, refining hydrogenation process R10 operating conditions altogether in oily coal is usually:
(2) refine hydrogenation process R10 altogether in oily coal, reaction temperature is 400~465 DEG C, reactor pressure be 6~
30MPa, gas-liquid volume ratio are 600~1500NL/kg, and deliquescence accelerant additive amount is 0.5~3 mass % of dry pulverized coal weight,
Co-catalyst additive amount is that the molar ratio of S/ catalyst activities metal in co-catalyst is 1.0~2.0, and coal slurry solid concentration is 45
~50 mass %.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, the hydrogenation catalyst that can be used, and is a kind of compound
Hydrogenation catalyst includes high-activity component and low activity component;The high-activity component metal and the weight of low activity component metals
Amount is than being 1: 10 to 10: 1;The high-activity component is the water soluble salt compound or its mixture of molybdenum;The low activity group
It is divided into ferric oxide ore or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and catalyst R10C water contents are less than
2wt%;R10C particle diameters are 1~100 μm of powdered granule.
Hydrogenation process R10 is refined in the present invention, (2) altogether in oily coal, and direct hydrogenation liquefaction of coal catalyst can surpass for nanometer
Fine grained aqua oxidation iron catalyst and/or iron oxide and/or pyrite and/or bloodstone and/or molybdenum oxide and/or molybdenum sulfide and/or
Ammonium molybdate and/or nickel sulfide.
The present invention in general, (2) refine hydrogenation process R10 altogether in oily coal, uses new hydrogen and/or recycle hydrogen;
(4) in short route recycled solvent oil hydrogenation modification reaction process R30, new hydrogen and/or recycle hydrogen are used;
(7) in solvent oil hydrogenation reaction process R20, new hydrogen and/or recycle hydrogen are used.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 1st kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 2nd kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF prepares solvent and be recycled back into oily coal and refine altogether by coal process for preparation M10 as coal slurry adds hydrogen anti-
Answer process R10.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 3rd kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by coal process for preparation M10 conducts
Coal slurry preparation solvent is recycled back into oily coal and refines hydrogenation process R10 altogether.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 4th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by hydro-upgrading process CR10UNIT
It is converted into the oily coal of hydrogen supply dissolvent oil CSH, CSH return rich in hydrogen supply hydrocarbon and refines hydrogenation process R10 altogether.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 5th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, and richness is converted by hydro-upgrading process
Hydrogen supply dissolvent the oil CSH, CSH of the hydrocarbon containing hydrogen supply prepare solvent as coal slurry by coal process for preparation M10 and are recycled back into oily coal
Refining hydrogenation process R10 altogether.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 6th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the hydro-upgrading process CR10UNIT of depitching distilled oil CFD, CFD that separating step obtains
High-pressure system, stablize the high-pressure system of reaction process R20 with solvent oil hydrogenation, partly or entirely share.
The present invention, can set the fluidisation pyrolytic process BR10UNIT of liquefied residue VS, and the 7th kind of flow scheme is:
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oil, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal as product raffinate VSP
Air and heat solution tar CF, pyrolysis char;
Pyrolytic tar CF passes through the hydro-upgrading process CR10UNIT of depitching distilled oil CFD, CFD that separating step obtains
High-pressure system, the high-pressure system with short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, partly or entirely share.
The present invention, (1) are non-coal derived oils, mainly by normal boiling point in coal process for preparation M10, feedstock oil SHVGO
Hydrocarbon composition higher than 530 DEG C.
The general control principle of the gas-phase presulfiding hydrogen concentration of the hydrogenation process of the present invention described in detail below.
As needed, any supplement sulphur can be added in any hydrogenation process, but be typically incorporated into most upstream
Hydrogenation process entrance, to ensure reaction process necessary minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm
(v) or specified value is expected, to ensure that the necessary hydrogen sulfide sectional pressure of catalyst is not less than minimum specified value.The supplement sulphur can
Be sulfide hydrogen or can be converted into hydrogen sulfide to material of the hydroconversion process without ill-effect, it is such as hydrogen sulfide containing
Gas or oil product or the generation molten sulfur of hydrogen sulfide or carbon disulfide or dimethyl disulfide etc. after being contacted with high-temperature hydrogen.
The rule of the high pressure separation process of the hydrogenation reaction effluent of the present invention described in detail below.
The high pressure separation process of hydrogenation reaction effluent generally comprises cold high pressure separator, when hydrocarbon in hydrogenation reaction effluent
Oil density big (for example being approached with water density) or viscosity are big or when being difficult to detach with water emulsification, it is also necessary to set operation temperature usual
For 150~450 DEG C of high pressure hot separator, hydrogenation reaction effluent enters high pressure hot separator and is separated into one in volume at this time
On the hot gas separated by high pressure separator gas that is mainly made of hydrogen and one be mainly made of conventional liq hydrocarbon and solid that may be present
Hot high score fluid body, hot gas separated by high pressure separator enter the cold high pressure separator that operation temperature is usually 20~80 DEG C be separated into cold high score oil and
Cold gas separated by high pressure separator since a large amount of high boiling components enter in hot high score fluid body, realizes following target:Cold high score oil density becomes smaller
Or viscosity becomes smaller or is easily isolated with water.The high pressure separation process setting high pressure hot separator of hydrogenation reaction effluent, is also equipped with
The advantages of reducing thermal loss because hot high score fluid body can be undergone to avoid hot gas separated by high pressure separator using air cooler or water cooler
Cool process.Meanwhile the hydrogenation process that the hot high score fluid body in part can be returned to upstream recycles, to improve
It receives the overall raw material property of the hydrogenation process of the recycle oil or cycle plus hydrogen is carried out to the recycle oil.
Hydrogenation reaction effluent or hot gas separated by high pressure separator enter before cold anticyclone separate section, usually first reduce temperature and (are usually
Feed and exchange heat with reactive moieties) (temperature should be higher than that in the hydrogenation reaction effluent gas phase that sulphur hydrogenates ammonia to about 220~100 DEG C
Crystallization temperature), then usually injection washings form water filling back end hydrogenation reaction effluent thereto, washings for absorbing ammonia and
Issuable other impurity such as hydrogen chloride etc., and the aqueous solution after absorbing ammonia necessarily absorbs hydrogen sulfide.In cold anticyclone separation unit
Point, the water filling back end hydrogenation reaction effluent is separated into:One the cold gas separated by high pressure separator being mainly made of in volume hydrogen, a master
Will by cold high score that conventional liq hydrocarbon and dissolved hydrogen form oil, one it is being mainly made of water and dissolved with ammonia, hydrogen sulfide it is cold
High score water.The cold high score water, the content of wherein ammonia are generally 0.5~15% (w), preferably 1~8% (w).Note washings
One purpose is the ammonia and hydrogen sulfide absorbed in hydrogenation reaction effluent, prevents from forming sulphur hydrogenation ammonia or more sulphur ammonia Crystallization Pluggings change
Hot device channel increases system pressure drop.The injection rate of the washings should be determined according to following principles:On the one hand, washings are noted
It is divided into vapour phase water and liquid phase water after entering hydrogenation reaction effluent, liquid phase water has to be larger than zero, preferably washs water inventory
30% or more;In another aspect, washings are used to absorb the ammonia in hydrogenation reaction effluent, the ammonia density of gas separated by high pressure separator is prevented too
Height reduces catalyst activity, and the lower the ammonia volumetric concentration of usual gas separated by high pressure separator the better, generally no greater than 200PPm (v), preferably less
In 50PPm (v).The cold high pressure separator operating pressure subtracts actual pressure drop, cold anticyclone for hydrogenation reaction partial pressure
The difference of separate section operating pressure and hydrogenation reaction pressure, it is unsuitable too low or excessively high, generally 0.35~3.2MPa, be usually
0.5~1.5MPa.The hydrogen volume concentration value of the cold gas separated by high pressure separator, should not too low (cause device operating pressure rise), one
As should be not less than 70% (v), preferably be not less than 80% (v), be preferably not below 85% (v).As previously described at least partially, usually
85~100% cold gas separated by high pressure separator is returned to be recycled in hydrogenation reaction part, to provide hydrogenation reaction part necessary amounts of hydrogen
And hydrogen concentration;In order to improve plant investment efficiency, it is necessary to assure cycle hydrogen concentration is not less than aforementioned lower limit value, for this purpose, according to
Specific feedstock property, reaction condition, product distribution can exclude a part of cold gas separated by high pressure separator to exclude the first that reaction generates
Alkane, ethane.For the cold gas separated by high pressure separator of discharge, conventional membrane separation process or pressure swing adsorption technique may be used or oil wash technique is real
Existing hydrogen and the separation of non-hydrogen gas component, and the hydrogen of recycling is used as new hydrogen.
New hydrogen enters plus hydrogen partial is to supplement the hydrogen of hydrogenation process consumption, and the higher the better for new hydrogen hydrogen concentration, generally
Not preferably less than 95% (v), preferably not below 99% (v).All new hydrogen can be introduced any hydrogenation reaction parts, be preferably introduced the
One hydrogenation reactor.
Embodiment
Embodiment one
100 tons/when raw material coal dust, 100 tons/when petroleum residual oil oily coal refine hydrogenation process altogether, it is preposition molten using the present invention
Agent oil stabilized hydrogenation reaction process R30 refines hydrogenation process R10 combined methods altogether with oily coal, and operating condition is as follows:
(1) in coal process for preparation M10, according to 1: 1 weight ratio raw material coal dust SF, 100 tons/when petroleum residual oil
SHVGO is made into coal R10F, and coal slurry solid concentration is 50 mass %;
(2) refine hydrogenation process R10 altogether in oily coal, reaction temperature is 400~455 DEG C, reaction pressure be 18~
20MPa, gas-liquid volume ratio are 700~800NL/kg, and deliquescence accelerant additive amount is 1.5~2 mass % of dry pulverized coal weight, is protected
It demonstrate,proves reaction compartment hydrogen sulphide in the vapor phase volumetric concentration and is more than 0.15%, the residence time is for 120~150 minutes (to raw material coal dust and stone
Dregs of fat oil total volume);
Hydrogenation process R10 is refined altogether in oily coal, and the hydrogenation catalyst used is a kind of composite hydrogenation catalyst, packet
Containing high-activity component and low activity component;The weight ratio of the high-activity component metal and low activity component metals is 1: 10 to 10
∶1;The high-activity component is the water soluble salt compound or its mixture of molybdenum;The low activity component is ultra-fine of nanometer
Grain aqua oxidation iron catalyst;
Oily coal refines hydrogenation process R10 altogether, comprising 3 order of reactions, uses gas-liquid separation step between grade, will detach liquid
Next stage reaction zone or cycle plus hydrogen are introduced, separation gas is drawn into reaction system without entering next stage reaction zone;Each reaction
Grade needs for example new hydrogen of the hydrogen material for adding in new low impurity content and/or recycle hydrogen;
1st, 2,3 order of reaction temperature are 400~420 DEG C, 420~435 DEG C, 440~455 DEG C;
1st, the residence time ratio of 2,3 order of reactions is 30%, 40%, 30%;
(3) in thermal high separation process R10P-HS, operation temperature is 410 DEG C, pressure is 18~20MPa;Oily coal refines altogether to be added
Hydrogen product R10P is separated into hot gas separated by high pressure separator R10P-HS-V and hot high score oil R10P-HS-L;
In thermal high separation process R10P-HS, air lift hydrogen R10P-HS-BV contact thermal high separation processes R10P- is used
Liquid existing for HS, with air lift low boiling component therein, gas stripping gas is eventually entered into hot gas separated by high pressure separator R10P-HS-V;
Hot gas separated by high pressure separator R10P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 400 DEG C;
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model changes for preposition online plus hydrogen
Property method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent plus hydrogen change
The thermal high separation process R30P-HS of property reaction process R30, R30 product R30P, comprises the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-
HS-V-MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
The operation temperature of warm high pressure separation process R10P-HS-V-MS is 180~280 DEG C;
Warm high score oil R10P-HS-V-MS-L is mainly made of hydro carbons of the normal boiling point between 250~400 DEG C;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the predecessor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of object R30F, in hydrogen, there are items for short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst
The reaction of at least part aromatic hydrogenation fractional saturation occurs under part, is converted into the product R30P rich in hydrogen supply hydrocarbon;
Stablize reaction process R30 in solvent oil hydrogenation, the normal boiling point of reaction effluent R30P is higher than 250 DEG C of hydro carbons:
It is 0.45~0.60 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,;Stablize reaction process in solvent oil hydrogenation
R30, the hydrogenation catalyst used are the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system;Reaction temperature is 340~360 DEG C, is added
Hydrogen pressure is 18~20MPa, and gas-liquid volume ratio is 600~800NL/kg;
4. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil
R30P-HS-L, the hot high score oil R30P-HS-L of at least part are used as logistics SR-DS, and the oily coal of multiple spot injection refines hydrogenation reaction mistake altogether
The different location of journey R10 can flexibly be injected into the starting reaction compartment of R10, intermediate reaction space, end reaction space;
The operation temperature of thermal high separation process R30P-HS is 180~280 DEG C;
Hot high score oil R30P-HS-L is mainly made of hydro carbons of the normal boiling point higher than 250 DEG C;
The weight flow and the weight flow of feedstock oil SF of short route cycle hydrogen supply dissolvent SR-DS, according to 2: 1 controls;
(5) in post processing system R10P-HS-V-AUNIT, separation and recovery hydrogen-rich gas XH obtain hydrogen-rich gas XHV and
Hydrocarbon ils XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process after hydrogen purification process, and (solvent oil hydrogenation is steady
Determine reaction process) it recycles, the hydrogen volume concentration for returning to hydrogenation process is more than 90%;
(6) liquefaction products fraction is obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Oily ML, the liquefied residue VS being mainly made of hydrocarbon of the normal boiling point higher than 520 DEG C.
Embodiment two
Based on embodiment one, increase following steps:
(7) stablize reaction process R20, under hydrogen, solvent oil hydrogenation catalyst existence condition, hydrogen supply in solvent oil hydrogenation
Hydrocarbon precursor R20F occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into the reaction effluent rich in hydrogen supply hydrocarbon
R20P;
Stablize reaction process R20 in solvent oil hydrogenation, the normal boiling point of reaction effluent R20P is higher than 250 DEG C of hydro carbons:
It is 0.45~0.60 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,;Stablize reaction process in solvent oil hydrogenation
R20, the hydrogenation catalyst used are the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system;Reaction temperature is 350~370 DEG C, is added
Hydrogen pressure is 18~20MPa, and gas-liquid volume ratio is 500~600NL/kg;
Hydrogen supply hydrocarbon precursor R20F, comprising at least part distillate oil ML, mainly by normal boiling point between 330~530 DEG C
Hydro carbons composition;
(8) in thermal high separation process R20P-HS, operation temperature is 230 DEG C, pressure is 18~20MPa;Solvent oil hydrogenation
Reaction product R20P is separated into hot gas separated by high pressure separator R20P-HS-V and hot high score oil R20P-HS-L;
Hot gas separated by high pressure separator R20P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 250 DEG C;
(9) in separation/fractionating section LR-DSF, heat of dissociation high score oil R20P-HS-L obtains long flow cycle hydrogen supply dissolvent
LR-DS;
The weight flow of hydrogen supply dissolvent LR-DS and the weight flow of feedstock oil SF, according to 0.5: 1 control;
30% hydrogen supply dissolvent LR-DS enters the second level reaction zone that oily coal refines hydrogenation process R10 altogether, 70% confession
Hydrogen solvent LR-DS enters the third level reaction zone that oily coal refines hydrogenation process R10 altogether.
Embodiment three
Based on embodiment one, increase following steps:
80% liquefied residue VS is as product raffinate VSP, and 20% liquefied residue VS is as liquefied residue cycle stock VSR
Oily coal is recycled back into as coal slurry preparation solvent refine hydrogenation process R10 altogether by coal process for preparation M10.
Example IV
Based on embodiment one, increase following steps:
Liquefied residue VS, into fluidisation pyrolytic process BR10UNIT, is converted into coal gas, pyrolysis coke as product raffinate VSP
Oily CF, pyrolysis char.
Embodiment five
Based on example IV, increase following steps:
Pyrolytic tar CF prepares solvent and be recycled back into oily coal and refine altogether by coal process for preparation M10 as coal slurry adds hydrogen anti-
Answer process R10.
Embodiment six
Based on example IV, increase following steps:
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by coal process for preparation M10 conducts
Coal slurry preparation solvent is recycled back into oily coal and refines hydrogenation process R10 altogether.
Embodiment seven
Based on embodiment six, increase following steps:
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by hydro-upgrading process CR10UNIT
It is converted into the oily coal of hydrogen supply dissolvent oil CSH, CSH return rich in hydrogen supply hydrocarbon and refines hydrogenation process R10 altogether.
Embodiment eight
Based on embodiment six, increase following steps:
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, and richness is converted by hydro-upgrading process
Hydrogen supply dissolvent the oil CSH, CSH of the hydrocarbon containing hydrogen supply prepare solvent as coal slurry by coal process for preparation M10 and are recycled back into oily coal
Refining hydrogenation process R10 altogether.
Embodiment nine
Based on embodiment seven, depitching distilled oil CFD, the CFD plus hydrogen that pyrolytic tar CF is obtained by separating step changes
The high-pressure system of matter process CR10UNIT stablizes the high-pressure system of reaction process R20 with solvent oil hydrogenation, partly or entirely altogether
With.
Embodiment ten
Based on embodiment seven, depitching distilled oil CFD, the CFD plus hydrogen that pyrolytic tar CF is obtained by separating step changes
The high-pressure system of matter process CR10UNIT, the high-pressure system with short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, part
Or it all shares.
Claims (64)
1. a kind of oily coal with short cycle hydrogen supply dissolvent oil is total to smelting method, it is characterised in that comprises the steps of:
(1) it is made into coal R10F in coal process for preparation M10, feedstock oil SHVGO, the coal dust SF of non-coal derived oils;
(2) refine hydrogenation process R10 altogether in oily coal, the short route recycled solvent oil SR-DS from step (4), hydrogen, can
The oily coal that can be used is refined altogether under hydrogenation catalyst existence condition, and coal R10F is converted into coal and refines hydrogenation products R10P altogether;
Refine hydrogenation process R10 altogether in oily coal, the swelling of coal occurs for the coal dust in coal R10F, be pyrolyzed, be hydrocracked plus
The lightings such as thermal cracking, stabilized hydrogenation reaction occurs for the Coal liquefactions such as stabilized hydrogen, the feedstock oil SHVGO in coal R10F,
Short route recycled solvent oil SR-DS is at least to the effect of pyrolysis free radical release reactive hydrogen;
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V and heat altogether
High score oil R10P-HS-L;
(4) it in short route recycled solvent oil hydrogenation modification process R30-UNIT, is reacted in short route recycled solvent oil hydrogenation modification
Process R30 under hydrogen, short route recycled solvent oil hydrogenation catalyst existence condition, includes hydrocarbon in hot gas separated by high pressure separator R10P-HS-V
The hydrogen supply hydrocarbon precursor R30F of component occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into rich in the anti-of hydrogen supply hydrocarbon
Answer effluent R30P;
High pressure stream comprising the hydrocarbon component in reaction effluent R30P is used as short route recycled solvent oil SR-DS, into oil
Coal refines hydrogenation process R10 altogether;
It is used as hydrogen-rich stream XH comprising the high pressure gas logistics for carrying out hydrogen in self-heating gas separated by high pressure separator R10P-HS-V;
(5) hydrogen-rich gas XHV and hydrocarbon ils are obtained in post processing system R10P-HS-V-AUNIT, separation and recovery hydrogen-rich gas XH
XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles.
2. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is the online hydrogenation modification side of postposition
Method, hot gas separated by high pressure separator R10P-HS-V are directly entered reaction process R30, and setting short route recycles the hydrogenation modification reaction process of solvent
Thermal high separation process R30P-HS, the delivery pump A-PUMP of R30, R30 product R30P, comprise the steps of:
1. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, urged in hydrogen, short route hydrogen supply dissolvent oil stabilized hydrogenation
Under agent existence condition, hot gas separated by high pressure separator R10P-HS-V enters reaction process R30 and switchs to the product R30P rich in hydrogen supply hydrocarbon, and heat is high
Divide the hydrocarbon component that gas R10P-HS-V is carried that the reaction of at least part aromatic hydrogenation fractional saturation occurs;
2. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil R30P-
HS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH, and the hot high score oil R30P-HS-L of at least part is through conveying
Enter oily coal as logistics SR-DS after pump A-PUMP pressurizations and refine hydrogenation process R10 altogether.
3. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is the online hydrogenation modification side of postposition
Method, hot gas separated by high pressure separator R10P-HS-V is in warm high score oil R10P-HS-V- isolated warm high pressure separation process R10P-HS-V-MS
MS-L enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, sets warm high pressure separation process R10P-HS-V-MS, system
The thermal high separation process R30P-HS of hydrogenation modification reaction process R30, the R30 product R30P of standby short route cycle solvent, conveying
A-PUMP is pumped, is comprised the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-HS-V-
MS-V and warm high score oil R10P-HS-V-MS-L;
Hot gas separated by high pressure separator R30P-HS-V is used as logistics XH at least partially;
2. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, urged in hydrogen, short route hydrogen supply dissolvent oil stabilized hydrogenation
Under agent existence condition, warm high score oil R10P-HS-V-MS-L enters reaction process R30 and is converted into the product rich in hydrogen supply hydrocarbon
The reaction of at least part aromatic hydrogenation fractional saturation occurs for R30P, the hydrocarbon component that hot gas separated by high pressure separator R10P-HS-V is carried;
3. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil R30P-
HS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH, and the hot high score oil R30P-HS-L of at least part is through conveying
Enter oily coal as logistics SR-DS after pump A-PUMP pressurizations and refine hydrogenation process R10 altogether.
4. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is preposition online hydrogenation modification side
Method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent hydrogenation modification it is anti-
The thermal high separation process R30P-HS of process R30, R30 product R30P is answered, is comprised the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-HS-V-
MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the precursor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of R30F, in hydrogen, short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst existence condition
Lower generation at least part aromatic hydrogenation fractional saturation reaction, is converted into the product R30P rich in hydrogen supply hydrocarbon;
4. in thermal high separation process R30P-HS, product R30P is separated into hot gas separated by high pressure separator R30P-HS-V and hot high score oil R30P-
HS-L, the hot high score oil R30P-HS-L of at least part enter oily coal as logistics SR-DS and refine hydrogenation process R10 altogether.
5. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, flow model is preposition online hydrogenation modification side
Method, set warm high pressure separation process R10P-HS-V-MS, delivery pump B-PUMP, prepare short route cycle solvent hydrogenation modification it is anti-
The thermal high separation process R30P-HS of process R30, R30 product R30P is answered, is comprised the steps of:
1. in warm high pressure separation process R10P-HS-V-MS, hot gas separated by high pressure separator R10P-HS-V is separated into warm gas separated by high pressure separator R10P-HS-V-
MS-V and warm high score oil R10P-HS-V-MS-L, the hot gas separated by high pressure separator R30P-HS-V of at least part are used as logistics XH;
2. in pressure process B-PUMP, warm high score oil R10P-HS-V-MS-L is after pump B-PUMP pressurizations as supercharging logistics
R10P-HS-V-MS-L-P enters short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30;
3. in short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30, the precursor as short route hydrogen supply dissolvent SR-DS
The supercharging logistics R10P-HS-V-MS-L-P of R30F, in hydrogen, short route hydrogen supply dissolvent oil stabilized hydrogenation catalyst existence condition
Lower generation at least part aromatic hydrogenation fractional saturation reaction is converted into the product R30P rich in hydrogen supply hydrocarbon, at least part heat
High score oil R30P-HS-L enters oily coal as logistics SR-DS and refines hydrogenation process R10 altogether.
6. according to the combined method described in Claims 2 or 3 or 4, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process R30P-HS, gas is used
Liquid existing for hydrogen R30P-HS-BV contact thermal high separation processes R30P-HS is carried, with air lift low boiling component therein, gas
Gas is carried to enter in hot gas separated by high pressure separator R30P-HS-V.
7. according to the combined method described in Claims 2 or 3 or 4, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process R30P-HS, hot high score
Oily R30P-HS-L is mainly made of hydro carbons of the normal boiling point higher than 280 DEG C.
8. according to the combined method described in Claims 2 or 3 or 4, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in thermal high separation process R30P-HS, hot high score
Oily R30P-HS-L is mainly made of hydro carbons of the normal boiling point higher than 230 DEG C.
9. according to the combined method described in Claims 2 or 3 or 4, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the operation temperature of thermal high separation process R30P-HS
It is 150~330 DEG C.
10. according to the combined method described in Claims 2 or 3 or 4, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the operation temperature of thermal high separation process R30P-HS
It is 180~280 DEG C.
11. according to the combined method described in Claims 2 or 3 or 4, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the operation temperature of thermal high separation process R30P-HS
It is 200~250 DEG C.
12. according to the combined method described in claim 3 or 4 or 5, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, in warm high pressure separation process R10P-HS-V-MS, make
Liquid existing for warm high pressure separation process R10P-HS-V-MS is contacted with air lift hydrogen R10P-HS-V-MS-BV, with air lift wherein
Low boiling component, gas stripping gas may finally be entered in warm gas separated by high pressure separator R10P-HS-V-MS-V.
13. according to the combined method described in claim 3 or 4 or 5, it is characterised in that:
(4) it is warm in warm high pressure separation process R10P-HS-V-MS in short route recycled solvent oil hydrogenation modification process R30-UNIT
High score oil R10P-HS-V-MS-L is mainly made of hydro carbons of the normal boiling point higher than 250 DEG C.
14. according to the combined method described in claim 3 or 4 or 5, it is characterised in that:
(4) it is warm in warm high pressure separation process R10P-HS-V-MS in short route recycled solvent oil hydrogenation modification process R30-UNIT
High score oil R10P-HS-V-MS-L is mainly made of hydro carbons of the normal boiling point higher than 200 DEG C.
15. according to the combined method described in claim 3 or 4 or 5, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the behaviour of warm high pressure separation process R10P-HS-V-MS
It is 150~330 DEG C to make temperature.
16. according to the combined method described in claim 3 or 4 or 5, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the behaviour of warm high pressure separation process R10P-HS-V-MS
It is 180~280 DEG C to make temperature.
17. according to the combined method described in claim 3 or 4 or 5, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the behaviour of warm high pressure separation process R10P-HS-V-MS
It is 200~250 DEG C to make temperature.
18. combined method according to claim 1, it is characterised in that:
(1) quality of pc concentration is more than 30% in coal process for preparation M10, coal slurry R10F.
19. combined method according to claim 1, it is characterised in that:
(1) quality of pc concentration is more than 40% in coal process for preparation M10, coal slurry R10F.
20. combined method according to claim 1, it is characterised in that:
(1) quality of pc concentration is more than 45% in coal process for preparation M10, coal slurry R10F.
21. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10, setting pre-hydrotreating reaction section R10-DD are refined altogether in oily coal;
In pre-hydrotreating reaction section R10-DD, coal R10F occurs pre-hydrotreating reaction and is converted into the pre- hydrogenation products R10-DD-P of coal,
Short route hydrogen supply dissolvent SR-DS plays a part of providing reactive hydrogen.
22. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10, setting pre-hydrotreating reaction section R10-DD are refined altogether in oily coal;
In pre-hydrotreating reaction section R10-DD, coal R10F occurs pre-hydrotreating reaction and is converted into pre- hydrogenation products R10-DD-P, short
Flow recycled solvent oil SR-DS plays a part of main offer reactive hydrogen.
23. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10, setting pre-hydrotreating reaction section R10-DD are refined altogether in oily coal;
In pre-hydrotreating reaction section R10-DD, coal R10F occurs pre-hydrotreating reaction and is converted into pre- hydrogenation products R10-DD-P, short
Flow recycled solvent oil SR-DS plays a part of main offer reactive hydrogen;
The hydrogen standard state volume of pre-hydrotreating reaction section R10-DD and the volume ratio of coal are less than 300: 1.
24. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, at least one intermediate product gas-liquid separation step R10-MS is set, that is, is set
The liquid stream material coal hydrogenation liquefaction reaction zone of at least two serial operation;
At least part gas-liquid separation step R10-MS discharges contain liquid phase material, into the liquid stream material coal hydrogenation liquefaction in downstream
Reaction zone;
The liquid stream material coal hydrogenation system for containing gaseous phase materials, not entering downstream of at least part gas-liquid separation step R10-MS discharges
Oily reaction zone.
25. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, on the basis of liquid stream material coal hydrogenation liquefaction reaction process, inject in batches
Hydrogen supply dissolvent, i.e., at least using 2 hydrogen-containing hydrocarbon stream addition points, the first hydrogen-containing hydrocarbon stream addition point is that oily coal refines hydrogenation reaction altogether
The starting reaction zone of process R10, the second hydrogen-containing hydrocarbon stream addition point are located at the downstream of the first hydrogen-containing hydrocarbon stream addition point.
26. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, on the basis of liquid stream material coal hydrogenation liquefaction reaction process, classification injection
Hydrogen supply dissolvent at least uses 2 hydrogen-containing hydrocarbon stream addition points, and the second hydrogen supply being mainly made of the higher hydrocarbon of normal boiling point
Hydrocarbon stream addition point is located at the downstream of the first hydrogen-containing hydrocarbon stream addition point being mainly made of the relatively low hydrocarbon of normal boiling point.
27. combined method according to claim 1, it is characterised in that:
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V and heat altogether
High score oil R10P-HS-L;
In thermal high separation process R10P-HS, deposited using air lift hydrogen R10P-HS-BV contacts thermal high separation process R10P-HS
Liquid, with air lift low boiling component therein.
28. combined method according to claim 1, it is characterised in that:
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V and heat altogether
High score oil R10P-HS-L;
In thermal high separation process R10P-HS, deposited using air lift hydrogen R10P-HS-BV contacts thermal high separation process R10P-HS
Liquid, with air lift low boiling component therein, gas stripping gas is eventually entered into hot gas separated by high pressure separator R10P-HS-V.
29. combined method according to claim 1, it is characterised in that:
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V and heat altogether
High score oil R10P-HS-L;
Hot gas separated by high pressure separator R10P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 450 DEG C.
30. combined method according to claim 1, it is characterised in that:
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V and heat altogether
High score oil R10P-HS-L;
Hot gas separated by high pressure separator R10P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 400 DEG C.
31. combined method according to claim 1, it is characterised in that:
(3) in thermal high separation process R10P-HS, coal refines hydrogenation products R10P and is separated into hot gas separated by high pressure separator R10P-HS-V and heat altogether
High score oil R10P-HS-L;
Hot gas separated by high pressure separator R10P-V, hydro carbons therein are mainly made of hydrocarbon of the normal boiling point less than 350 DEG C.
32. combined method according to claim 1, it is characterised in that:
(5) it in post processing system R10P-HS-V-AUNIT, separates and recovers hot hydrogen-rich gas XH and obtains hydrogen-rich gas XHV and hydrocarbon
Oily XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles, the hydrogen of hydrogen-rich gas hydrogen-rich gas XHV
Volumetric concentration is more than 70%.
33. combined method according to claim 1, it is characterised in that:
(5) it in post processing system R10P-HS-V-AUNIT, separates and recovers hot hydrogen-rich gas XH and obtains hydrogen-rich gas XHV and hydrocarbon
Oily XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles, the hydrogen of hydrogen-rich gas hydrogen-rich gas XHV
Volumetric concentration is more than 80%.
34. combined method according to claim 1, it is characterised in that:
(5) it in post processing system R10P-HS-V-AUNIT, separates and recovers hot hydrogen-rich gas XH and obtains hydrogen-rich gas XHV and hydrocarbon
Oily XHL;At least part hydrogen-rich gas XHV returns to hydrogenation process and recycles, the hydrogen of hydrogen-rich gas hydrogen-rich gas XHV
Volumetric concentration is more than 90%.
35. combined method according to claim 1, it is characterised in that:
(5) it in post processing system R10P-HS-V-AUNIT, separates and recovers hot hydrogen-rich gas XH and obtains hydrogen-rich gas XHV and hydrocarbon
Oily XHL;Hydrogenation process is returned after at least part hydrogen-rich gas XHV purifying hydrogen of hydrogen to recycle.
36. combined method according to claim 1, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
A part of liquefied residue VS enters oily coal as cycle raffinate VSR and refines hydrogenation process R10 altogether.
37. combined method according to claim 1, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 530 DEG C;
A part of liquefied residue VS enters oily coal as cycle raffinate VSR and refines hydrogenation process R10 altogether.
38. combined method according to claim 1, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;
Partial liquefaction residue VS is recycled back into oily coal as liquefied residue cycle stock VSR and is total to as product VSP, partial liquefaction residue
Refine hydrogenation process R10.
39. combined method according to claim 1, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;
Partial liquefaction residue VS is prepared as product VSP, partial liquefaction residue as liquefied residue cycle stock VSR by coal
Process M10 is recycled back into oily coal as coal slurry configuration solvent naphtha and refines hydrogenation process R10 altogether.
40. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing, be 1 tunnel or 2 tunnels or
Multichannel material.
41. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogen supply hydrocarbon precursor of processing is 2 tunnels or multichannel
Material adds hydrogen mode using the synchronization of mixed raw material hydrocarbon.
42. combined method according to claim 1, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, before the hydrogen supply hydrocarbon precursor of processing is 2 hydrogen supply hydrocarbon
Body object, the boiling range of 2 hydrogen supply hydrocarbon precursors, molecular structure differ greatly, the asynchronous plus hydrogen side that this 2 road hydrocarbon stream uses at this time
1 kind or several in following method of formula:
1. the first hydrogen supply hydrocarbon precursor adds together after hydrogenation products pre- obtained by pre-add hydrogen are mixed with the second hydrogen supply hydrocarbon precursor
Hydrogen;
Products therefrom mixing detaches together after 2. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add hydrogen respectively;
3. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add respectively after hydrogen after products therefrom mixing together again plus
Hydrogen;
4. the first hydrogen supply hydrocarbon precursor, products therefrom carries out thermal high separation respectively after the second hydrogen supply hydrocarbon precursor adds hydrogen respectively,
At least part of each hot high score oil enters oily coal and refines hydrogenation process R10 altogether.
43. combined method according to claim 1, it is characterised in that:
(6) in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L obtain be by normal boiling point mainly
250~530 DEG C of liquefaction products distillates, liquefied residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500
℃;
(7) in solvent oil hydrogenation reaction process R20, under hydrogen, solvent oil hydrogenation catalyst existence condition, hydrogen supply hydrocarbon precursor
R20F occurs the reaction of at least part aromatic hydrogenation fractional saturation and is converted into the reaction effluent R20P rich in hydrogen supply hydrocarbon;
Hydrogen supply hydrocarbon precursor R20F, includes at least part distillate oil ML;
In solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 1 tunnel or 2 tunnels or multichannel material;
(8) separation reaction effluent R20P obtains long flow cycle hydrogen supply dissolvent LR-DS;
At least part hydrogen supply dissolvent LR-DS enters oily coal and refines hydrogenation process R10 altogether.
44. combined method according to claim 1, it is characterised in that:
(7) in solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 2 tunnels or multichannel material, using mixing original
The synchronization of material hydrocarbon adds hydrogen mode.
45. combined method according to claim 1, it is characterised in that:
(7) in solvent oil hydrogenation reaction process R20, the hydrogen supply hydrocarbon precursor of processing is 2 hydrogen supply hydrocarbon precursors, 2 hydrogen supply hydrocarbon
The boiling range of precursor, molecular structure differ greatly, and the asynchronous plus hydrogen mode that this 2 road hydrocarbon stream uses at this time is selected from following method
In a kind or several:
1. the first hydrogen supply hydrocarbon precursor adds together after hydrogenation products pre- obtained by pre-add hydrogen are mixed with the second hydrogen supply hydrocarbon precursor
Hydrogen;
Products therefrom mixing detaches together after 2. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add hydrogen respectively;
3. the first hydrogen supply hydrocarbon precursor, the second hydrogen supply hydrocarbon precursor parallel connection add respectively after hydrogen after products therefrom mixing together again plus
Hydrogen;
4. the first hydrogen supply hydrocarbon precursor, products therefrom carries out thermal high separation respectively after the second hydrogen supply hydrocarbon precursor adds hydrogen respectively,
At least part mixing of each hot high score oil is latter and enters separation/fractionating section LR-DSF.
46. combined method according to claim 1, it is characterised in that:
(2) oily coal refines a kind or several of the group of the mode of operation of the reactor that hydrogenation process R10 is used in following altogether
It closes:
1. suspension bed, that is, slurry bed system;
2. ebullated bed;
3. slight expanded-bed.
47. combined method according to claim 1, it is characterised in that:
(4) mode of operation of hydrogenation reactor that short route recycled solvent oil hydrogenation modification process R30-UNIT is used is selected from following
In a kind or several of combination:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalyst of activity from bed bottom in an intermittent fashion, with
The mode of interval fills into fresh catalyst from bed top and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
48. combined method according to claim 43, it is characterised in that:
(7) a kind or several of group of the mode of operation for the reactor that solvent oil hydrogenation reaction process R20 is used in following
It closes:
1. floating bed hydrogenation reactor;
2. boiling bed hydrogenation reactor usually draws off the decreased catalyst of activity from bed bottom in an intermittent fashion, with
The mode of interval fills into fresh catalyst from bed top and maintains bed catalyst reserve;
3. up flow type slight expanded-bed;
It is 4. upflow fixed bed;
5. down-flow fixed bed;
6. the low liquid phase systemic circulation hydrogenation reactor of hydrogen to oil volume ratio.
49. combined method according to claim 43, it is characterised in that:
(4) the conventional boiling in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route recycled solvent oil SR-DS
Point is higher than 250 DEG C of hydro carbons:It is 0.35~0.70 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 15%, aromatic carbon rate,;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Part is full
It is 0.35~0.70 to be more than 15%, aromatic carbon rate with the weight content of aromatic hydrocarbons.
50. combined method according to claim 43, it is characterised in that:
(4) the conventional boiling in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route recycled solvent oil SR-DS
Point is higher than 250 DEG C of hydro carbons:It is 0.40~0.65 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 20%, aromatic carbon rate,;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Part is full
It is 0.40~0.65 to be more than 20%, aromatic carbon rate with the weight content of aromatic hydrocarbons.
51. combined method according to claim 43, it is characterised in that:
(4) the conventional boiling in short route recycled solvent oil hydrogenation modification process R30-UNIT, short route recycled solvent oil SR-DS
Point is higher than 250 DEG C of hydro carbons:It is 0.45~0.60 that the weight content of fractional saturation aromatic hydrocarbons, which is more than 25%, aromatic carbon rate,;
(7) normal boiling point in solvent oil hydrogenation reaction process R20, reaction effluent R20P is higher than 250 DEG C of hydro carbons:Part is full
It is 0.45~0.60 to be more than 25%, aromatic carbon rate with the weight content of aromatic hydrocarbons.
52. combined method according to claim 43, it is characterised in that:
(4) in short route recycled solvent oil hydrogenation modification process R30-UNIT, the hydrogenation catalyst used for Ni-Mo, Ni-Co or
The hydrogenation catalyst of Ni-W systems;Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, gas-liquid volume ratio for 300~
1000NL/kg;
(7) in solvent oil hydrogenation reaction process R20, the hydrogenation catalyst used is Ni-Mo, Ni-Co or Ni-W system plus hydrogen is urged
Agent;Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000NL/kg.
53. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, reaction temperature is 400~465 DEG C, reactor pressure is 6~30MPa, gas
Liquid volume ratio be 600~1500NL/kg, deliquescence accelerant additive amount be dry pulverized coal weight 0.5~3 mass %, co-catalyst
Additive amount is that the molar ratio of S/ catalyst activities metal in co-catalyst is 1.0~2.0, and coal slurry solid concentration is 45~50 matter
Measure %.
54. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, the hydrogenation catalyst used is a kind of composite hydrogenation catalyst, comprising
High-activity component and low activity component;The high-activity component metal and the weight ratio of low activity component metals are 1: 10 to 10:
1;The high-activity component is the water soluble salt compound or its mixture of molybdenum;The low activity component for ferric oxide ore or
Iron sulfide ore, wherein iron in ore content are not less than 40wt%, and catalyst R10C water contents are less than 2wt%;R10C particles are straight
Diameter is 1~100 μm of powdered granule.
55. combined method according to claim 1, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, direct hydrogenation liquefaction of coal catalyst is nanometer ultra-fine grain hydrated ferric oxide
Catalyst and/or iron oxide and/or pyrite and/or bloodstone and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.
56. combined method according to claim 43, it is characterised in that:
(2) hydrogenation process R10 is refined altogether in oily coal, use new hydrogen and/or recycle hydrogen;
(4) in short route recycled solvent oil hydrogenation modification reaction process R30, new hydrogen and/or recycle hydrogen are used;
(7) in solvent oil hydrogenation reaction process R20, new hydrogen and/or recycle hydrogen are used.
57. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char.
58. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char;
Pyrolytic tar CF is recycled back into oily coal as coal slurry preparation solvent by coal process for preparation M10 and refines hydrogenation reaction mistake altogether
Journey R10.
59. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, by coal process for preparation M10 as coal slurry
Preparation solvent is recycled back into oily coal and refines hydrogenation process R10 altogether.
60. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, and is converted by hydro-upgrading process CR10UNIT
The oily coal of hydrogen supply dissolvent oil CSH, CSH return to be rich in hydrogen supply hydrocarbon refines hydrogenation process R10 altogether.
61. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char;
Pyrolytic tar CF passes through the depitching distilled oil CFD that separating step obtains, and is converted by hydro-upgrading process rich in confession
Hydrogen supply dissolvent the oil CSH, CSH of hydrogen hydrocarbon are recycled back into oily coal as coal slurry preparation solvent by coal process for preparation M10 and refine altogether
Hydrogenation process R10.
62. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char;
Pyrolytic tar CF passes through the height of the hydro-upgrading process CR10UNIT of depitching distilled oil CFD, CFD that separating step obtains
Pressure system is stablized the high-pressure system of reaction process R20 with solvent oil hydrogenation, is partly or entirely shared.
63. combined method according to claim 36, it is characterised in that:
(6) liquefaction products distillate, liquid are obtained in separation/fractionating section R10P-HS-L-DS, heat of dissociation high score oil R10P-HS-L
Change residue VS;The normal boiling point of most of hydro carbons in liquefied residue VS is higher than 500 DEG C;
At least part liquefied residue VS is as product raffinate VSP, into fluidisation pyrolytic process BR10UNIT, be converted into coal gas,
Pyrolytic tar CF, pyrolysis char;
Pyrolytic tar CF passes through the height of the hydro-upgrading process CR10UNIT of depitching distilled oil CFD, CFD that separating step obtains
Pressure system, the high-pressure system with short route hydrogen supply dissolvent oil stabilized hydrogenation reaction process R30 partly or entirely share.
64. combined method according to claim 1, it is characterised in that:
(1) in coal process for preparation M10, feedstock oil SHVGO, it is non-coal derived oils, is mainly higher than 530 DEG C by normal boiling point
Hydrocarbon forms.
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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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