CN115011384B - Process and device for preparing synthetic petroleum - Google Patents
Process and device for preparing synthetic petroleum Download PDFInfo
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- CN115011384B CN115011384B CN202210654688.XA CN202210654688A CN115011384B CN 115011384 B CN115011384 B CN 115011384B CN 202210654688 A CN202210654688 A CN 202210654688A CN 115011384 B CN115011384 B CN 115011384B
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- 239000003208 petroleum Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title abstract description 31
- 230000008569 process Effects 0.000 title abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 48
- 239000002028 Biomass Substances 0.000 claims abstract description 45
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 36
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 230000006698 induction Effects 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 95
- 239000007788 liquid Substances 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910003294 NiMo Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910017262 Mo—B Inorganic materials 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 241000195493 Cryptophyta Species 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000010775 animal oil Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000010690 paraffinic oil Substances 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 2
- 239000010779 crude oil Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229940008163 petroleum preparation Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a preparation process and a device for synthesizing petroleum, wherein the process comprises the following steps of S1, carrying out catalytic hydrodeoxygenation reaction on prepared oil raw materials to obtain a first-stage product; s2, mixing the primary product with template petroleum according to a preset mass ratio, and then carrying out supermolecule template induction synthesis reaction under a high pressure condition of 40-80MPa to obtain synthetic petroleum. According to the invention, the oil raw material is pretreated through the catalytic hydrogenation process, and then the quality of the biomass oil is greatly improved after deep processing through the supermolecular compound synthesis process, so that all oxygen-containing compounds in the biomass oil can be converted into hydrocarbon without oxygen, and meanwhile, the hydrocarbon ratio and the heat value of the biomass oil can be improved, and the quality index of the synthesized composite biomass oil can reach the standard of conventional petroleum.
Description
Technical Field
The invention relates to the technical field of synthetic petroleum preparation, in particular to a preparation process and a device of synthetic petroleum.
Background
The problem of petroleum shortage creates a global energy crisis, and finding a suitable alternative energy attracts more and more attention. Of the many petroleum supplementary and alternative fuels, only biomass oil belongs to renewable energy sources and can form a huge industry like coal, petroleum and natural gas for substantial production. The biomass oil has the advantages of wide raw material sources, multiple varieties, large reserves, regeneration, zero carbon circulation emission and the like, and becomes a novel energy source with great development prospect, so that the utilization and development of the biomass oil have become a hot spot for domestic and foreign research.
To date, research and development of biomass oil is limited to refining of biomass oil, for example, biomass oil is modified by catalytic hydrogenation, catalytic cracking, catalytic esterification, steam reforming, emulsification and other methods and then is used for preparing biodiesel or fuel oil, research and patents for directly using the biomass oil after modification for petroleum substitution do not appear, and most importantly, the problem of difference between high oxygen content, low heat value and the like of the biomass oil and conventional petroleum is not solved.
At present, synthetic oil is mostly prepared by Fischer-Tropsch synthesis, for example, patent CN201210214746.3 discloses a method for biologically synthesizing oil products and chemicals, and raw material gas is oxidized and deacidified to obtain converted gas; and (3) gasifying and deacidifying the raw materials to obtain synthesis gas, and carrying out Fischer-Tropsch synthesis reaction on the converted gas and the synthesis gas to obtain heavy oil, light oil, crude wax, synthetic water and synthetic tail gas. The product obtained by the method has larger difference with petroleum crude oil in quality, and has low recycling value.
In view of the foregoing, there is a need for an improved process and apparatus for the preparation of synthetic petroleum to solve the above-mentioned problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation process and a device for synthesizing petroleum, which take composite biomass oil as a raw material, use a catalytic hydrogenation process as a pretreatment section, and deeply process the biomass oil through a supermolecular compound synthesis process, so that the quality of the biomass oil is greatly improved, and the invention provides a synthesis technology for completely converting oxygen-containing compounds in the biomass oil into hydrocarbon without oxygen, and simultaneously improving the hydrocarbon ratio and the heat value of the biomass oil, so that the quality index of the synthesized composite biomass oil reaches the standard of conventional petroleum.
In order to achieve the above object, the present invention provides a process for preparing synthetic petroleum, comprising the steps of:
s1, carrying out catalytic hydrodeoxygenation reaction on the prepared oil raw materials to obtain a first-stage product;
s2, mixing the primary product with template petroleum according to a preset mass ratio, and then carrying out supermolecular template induction synthesis reaction under a high-pressure condition to obtain the synthetic petroleum.
As a further improvement of the present invention, in step S2, the preset mass ratio of the primary product to the template oil is (2:8) - (5:5).
As a further improvement of the invention, in the step S2, the temperature of the supermolecular template for inducing the synthesis reaction is 60-80 ℃, the pressure is 40-80MPa, and the time is 1-10h.
As a further improvement of the invention, in the step S2, the catalysts for the supermolecular template induced synthesis reaction are NiMo/HZSM-5 and NiMo/TiO 2 One of them.
As a further improvement of the present invention, in step S1, the catalytic hydrodeoxygenation reaction comprises: adding 3-5MPa hydrogen, and then reacting at 200-280 deg.C and 5-8MPa for 1-5h, preferably 1-3h.
As a further improvement of the present invention, in step S1, the catalyst for the catalytic hydrodeoxygenation reaction is Co-Mo-B or Ni-Mo-B.
As a further improvement of the present invention, in step S1, the oil raw material includes one or more of biomass oil, animal oil, household garbage oil, plastic oil, rubber oil; the biomass oil comprises straw oil and algae oil.
As a further improvement of the present invention, the oil feedstock comprises at least two types of oils, and the oil feedstock is formulated and mixed in a predetermined synthetic petroleum composition and yield.
A preparation device for synthesizing petroleum comprises a raw material catalytic hydrogenation system and a supermolecule synthesis system; the catalytic hydrogenation system comprises a catalytic hydrogenation reactor, a liquid high-pressure pump and a hydrogen booster pump which are connected with a charging end of the catalytic hydrogenation reactor, and a cooler and a separator which are connected with a discharging end of the catalytic hydrogenation reactor; the supermolecule synthesis system comprises a supermolecule synthesis reactor, a liquid high-pressure pump and a template petroleum high-pressure pump which are connected with the feed end of the supermolecule synthesis reactor, and a separator connected with the discharge end of the supermolecule synthesis reactor.
As a further improvement of the invention, the catalytic hydrogenation system further comprises a proportioning and blending system connected with the liquid high-pressure pump of the catalytic hydrogenation system, wherein the proportioning and blending system comprises a proportioning storage tank and a mixing tank which are sequentially connected.
The beneficial effects of the invention are as follows:
1. the preparation process and the device for synthesizing the petroleum provided by the invention take the composite biomass oil as a raw material, use a catalytic hydrogenation process as a pretreatment section, and deeply process the biomass oil through a supermolecular compound synthesis process, so that the quality of the biomass oil is greatly improved, the synthesis technology for converting all oxygen-containing compounds in the biomass oil into hydrocarbon without oxygen is provided, and simultaneously the hydrocarbon ratio and the heat value of the biomass oil are improved, so that the quality index of the synthesized composite biomass oil reaches the standard of conventional petroleum.
2. The invention can promote the transformation of the initial hydrocarbon trend to be more consistent with the crude oil structure of the petroleum by the high pressure action and the induction of the template petroleum, thereby obtaining the synthetic petroleum with the quality index (hydrocarbon ratio, heat value and the like) similar to the standard of the conventional petroleum and having remarkable economic value.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus for preparing synthetic petroleum according to the present invention.
Reference numerals
1-proportioning a storage tank; 2-stirring and mixing tank; 3-a first liquid high pressure pump; 4-a catalytic hydrogenation reaction tank; 4.1-heating jacket; 5-a hydrogenation booster pump; a 6-cooler; 7-a separation tank; 7.1-a liquid outlet; 7.2-exhaust port; 8-a buffer tank; 9-a second liquid high pressure pump; 10-a supermolecule synthesis reactor; 10.1-heating means; 11-a template petroleum pump; 12-separator; 13, a discharge hole; 14-control system.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific embodiments.
It should be further noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the specific embodiments, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation process of synthetic petroleum, which comprises the following steps:
s1, carrying out catalytic hydrodeoxygenation reaction on the prepared oil raw materials to obtain a first-stage product;
s2, mixing the primary product with template petroleum according to a preset mass ratio, and then carrying out supermolecular template induction synthesis reaction under a high-pressure condition to obtain the synthetic petroleum.
Usually, after the reaction is finished, the mixture enters a separation process, is cooled to 40-60 ℃, is depressurized to <1MPa and is discharged.
In the operation, the oil raw material is subjected to catalytic hydrodeoxygenation reaction to remove most of oxygen and is converted into initial hydrocarbon (primary product); then the synthesis reaction is induced by the supermolecular template, and under the induction of template petroleum, the initial hydrocarbon is assembled with the template petroleum to obtain the synthesized petroleum. In the step, through the high pressure action and the induction of template petroleum, the transformation of the initial hydrocarbon trend to be more consistent with the petroleum crude oil structure can be promoted, so that the synthetic petroleum with the quality index (hydrocarbon ratio, heat value and the like) similar to the conventional petroleum standard can be obtained, and the economic value is obvious. Template petroleum is paraffinic, structurally close to natural petroleum, paraffinic, naphthenic, aromatic, and minor amounts of fatty acids, mercaptans, gums, waxy and inorganic.
In step S2, the preset mass ratio of the primary product to the template petroleum is (2:8) - (5:5), preferably (3:7) - (4:6). The temperature of the supermolecular template induced synthesis reaction is 60-80 ℃, the pressure is 20-80MPa, preferably 40-80MPa, more preferably 50-60MPa; the time is 1 to 10 hours, preferably 1 to 8 hours, more preferably 1 to 5 hours, and still more preferably 1 to 2 hours.
In the step S2, the catalysts for the supermolecular template induced synthesis reaction are NiMo/HZSM-5 and NiMo/TiO 2 One of them.
In step S1, the catalytic hydrodeoxygenation reaction comprises: adding 3-5MPa hydrogen, and then reacting at 200-280 deg.C and 5-8MPa for 1-5h, preferably 1-3h.
The catalyst for the catalytic hydrodeoxygenation reaction is Co-Mo-B or Ni-Mo-B.
The oil raw materials comprise one or more of biomass oil, animal oil, household garbage oil, plastic oil and rubber oil; the biomass oil comprises straw oil and algae oil. The oil raw materials at least comprise two types of oil, and the oil raw materials are blended and mixed according to the preset composition and yield of the synthetic petroleum.
As shown in FIG. 1, the invention also provides a preparation device for synthesizing petroleum, which comprises a raw material catalytic hydrogenation system and a supermolecule synthesis system; the catalytic hydrogenation system comprises a catalytic hydrogenation reactor, a liquid high-pressure pump and a hydrogen booster pump which are connected with a charging end of the catalytic hydrogenation reactor, and a cooler and a separator which are connected with a discharging end of the catalytic hydrogenation reactor; the supermolecule synthesis system comprises a supermolecule synthesis reactor, a liquid high-pressure pump and a template petroleum high-pressure pump which are connected with the feed end of the supermolecule synthesis reactor, and a separator connected with the discharge end of the supermolecule synthesis reactor. The catalytic hydrogenation reactor and the supermolecule synthesis reactor are both sleeved with heating devices.
The catalytic hydrogenation system comprises a catalytic hydrogenation system, and is characterized by further comprising a proportioning and blending system connected with a liquid high-pressure pump of the catalytic hydrogenation system, wherein the proportioning and blending system comprises a proportioning storage tank 1 and a mixing tank 2 which are sequentially connected.
In actual operation, the configuration software of the control system 14 can perform bus control on each route parameter, and can be simultaneously connected with the internet of things for remote monitoring.
The working principle is as follows: and respectively placing more than 2 kinds of biomass oil such as straw oil, algae oil, household garbage oil, plastic oil, rubber oil and the like into a proportioning storage tank 1 in a proportioning and blending system, outputting oil mass into a stirring and mixing tank 2 according to data required by design for blending, wherein the blending and stirring speed is 60-120 r/min, and the stirring time is 10-20min. The catalyst enters a catalytic hydrogenation reaction tank 4 through a liquid high-pressure pump 3, an auxiliary heating sleeve 4.1 heats the reactor to 200-280 ℃, a hydrogenation booster pump 5 is started, and H is added 2 Pressurizing to 3-5MPa. After the oil delivery pressure is regulated to 5-8MPa by the liquid high-pressure pump 3, the pressure maintaining reaction is carried out for 1-2h, the gas-liquid mixture of the reactor enters the separation tank 7 through the cooler 6, the separation temperature is 80-150 ℃, the separation pressure is 3-5MPa, the separation time is 1h, the oil liquid of the gas-liquid mixture is discharged from 7.1 to the buffer tank 8 and enters the supermolecule synthesis system, and the gas in the mixture is discharged from the gas outlet 7.2.
The biomass oil entering the buffer tank 8 is conveyed into the supermolecule synthesis reactor 10 through the liquid high-pressure pump 9, and meanwhile, the template petroleum pump 11 adds template petroleum into the synthesis reactor 10 to be mixed with the biomass oil, the auxiliary heating device 10.1 of the reactor 10 is heated to the reaction temperature of 60-80 ℃, the reaction pressure of 40-80MPa, and the reaction time of 1-2h. The supramolecular compounds formed after the reaction are separated in a separator 12 and discharged at a lower discharge opening 13 of the separator.
Example 1
A process for the preparation of synthetic petroleum comprising the steps of:
(1) Proportioning straw oil and plastic oil according to a mass ratio of 1:1, fully stirring and mixing, and conveying to a catalytic hydrogenation process by using a high-pressure pump; ni-Mo-B is selected as a catalyst; heating to 260 ℃;
wherein, hydrogen with the pressure of 3-4Mpa is added, and biomass oil with the pressure of 5-8Mpa is added; after 1-2h of reaction, separating, wherein the separating temperature is 120 ℃, the separating pressure is 3-5Mpa, and the separating time is 1h.
(2) The separated biomass oil enters a supermolecule synthesis process through a buffer storage tank, and the mass ratio of the separated biomass oil to template petroleum is 4:6; supermolecule synthesis conditions: the temperature is 60-80 ℃, the pressure is 60MPa, and the reaction time is 2h. The heterogeneous catalyst used in supermolecule synthesis is NiMo/HZSM-5 or NiMo/TiO 2 。
(3) After the reaction is finished, the mixture enters a separation process, is cooled to 40-60 ℃, is depressurized to <1MPa, and is discharged.
TABLE 1 comparison of properties of synthetic petroleum with conventional crude oil
As can be seen from table 1, 1. Color: the conventional crude oil has black, brown, colorless, etc. The color of the synthesized petroleum is black brown, which is similar to that of the domestic conventional crude oil.
2. Viscosity: the synthetic petroleum is detected to be 70.71 according to the kinematic viscosity standard, the average value of the domestic conventional petroleum reaches 180, and the synthetic petroleum is close to the 83.36 value of the crude oil of the victory oil field.
3. Heating value: i.e., calorific value, is an important indicator of petroleum properties. The synthetic petroleum was 41.32MJ/Kg, while the average value of the conventional crude oil was 41.816/MJ/Kg, and the values differed by only 0.49MJ/Kg.
4. Moisture content: the detection value of the synthetic petroleum is less than 0.05% and is much lower than the value of 0.1-0.75 of the conventional crude oil.
5. Element composition evaluation: the crude oil element mainly comprises carbon, hydrogen, oxygen, nitrogen and sulfur, and is the most important index for measuring the properties of crude oil. The conventional crude oil has 83-87% carbon, 10.9-14% hydrogen, 0.08-1082% oxygen, 0.02-1.7% nitrogen and 0.06-0.8% sulfur. 89.82% of the synthetic petroleum C is slightly higher than the conventional crude oil, 9.30% of H is slightly lower than the conventional petroleum, 0.07% of O is lower than the conventional petroleum, 0.25% of N and 0.556% of S are consistent with the conventional petroleum index. The sulfur content is close to the 0.52% content index of crude oil in the crude oil field.
6. Density: the synthetic petroleum is 1000.6 kg/square meter, which is slightly higher than the 850-1000 range of the conventional crude oil, which indicates that the light oil accounts for slightly lower proportion and the proportion of the light oil needs to be increased.
7. Condensation point: the synthetic petroleum is at the temperature of minus 10 ℃ and has a lower condensation point, but the synthetic petroleum has less wax in the normal index range of crude oil, thus being suitable for transportation.
8. Carbon residue: the residual carbon is 7.5% and belongs to the normal petroleum index range.
9. Trace metal content: the trace metals content in synthetic petroleum is generally less than conventional crude oil because the trace metals are accumulated in ash after pyrolysis of biomass.
Therefore, the treatment method has obvious application value and is convenient for being put into practical production.
Examples 2-3 and comparative examples 1-2
The preparation process of synthetic petroleum is different from that of example 1 in that the mass ratio of the biomass oil separated in the supramolecular synthesis process to the template petroleum is shown in table 2, and the other steps are substantially the same as those of example 1, and are not repeated here.
TABLE 2 mass ratios and index parameters for examples 2-3 and comparative examples 1-2
| Sample preparation | Mass ratio | Heating value MS/KG |
| Example 2 | 5:5 | 40.01 |
| Example 3 | 2:8 | 41.43 |
| Comparative example 1 | 6:4 | 37.22 |
| Comparative example 2 | 10:0 | 32.01 |
From Table 2, it can be seen that when the template oil content is too small, the heating value of the obtained synthetic oil is significantly reduced, and it can be seen that the invention has an important effect on the synthetic reaction through template oil induction.
Examples 4 to 6
The process for preparing synthetic petroleum is different from example 1 in that the pressure of the supramolecular synthesis process is shown in table 3, and the other processes are substantially the same as in example 1, and will not be described again.
TABLE 3 mass ratios and index parameters for examples 4-6
| Sample preparation | Pressure (MPa) | Heating value MS/KG |
| Example 4 | 20 | 39.21 |
| Example 5 | 40 | 40.15 |
| Example 6 | 80 | 41.03 |
It can be seen from table 3 that the pressure of supermolecule induced synthesis also has a significant impact on the quality of the synthetic petroleum. According to the invention, the synthetic petroleum with excellent quality is obtained through petroleum template petroleum induction and matching with proper process conditions, and the method has important value for secondary utilization of energy.
In summary, the preparation process and the device for synthesizing the petroleum provided by the invention take the composite biomass oil as a raw material, use a catalytic hydrogenation process as a pretreatment section, and deeply process the biomass oil through a supermolecular compound synthesis process, so that the quality of the biomass oil is greatly improved, the synthesis technology for converting all oxygen-containing compounds in the biomass oil into hydrocarbon without oxygen and improving the hydrocarbon ratio and the heat value of the biomass oil is provided, and the quality index of the synthesized composite biomass oil reaches the standard of conventional petroleum.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The preparation process of the synthetic petroleum is characterized by comprising the following steps of:
s1, carrying out catalytic hydrodeoxygenation reaction on the prepared oil raw materials to obtain a first-stage product; the catalytic hydrodeoxygenation reaction comprises: adding 3-5MPa hydrogen, and then reacting for 1-5h at 200-280 ℃ under 5-8MPa; the catalyst for the catalytic hydrodeoxygenation reaction is Co-Mo-B or Ni-Mo-B; the oil raw materials comprise one or more of biomass oil, animal oil, household garbage oil, plastic oil and rubber oil; the biomass oil comprises straw oil or algae oil;
s2, mixing the primary product with template petroleum according to a preset mass ratio, and then carrying out supermolecular template induction synthesis reaction under a high-pressure condition to obtain synthetic petroleum;
in step S2, the preset mass ratio of the primary product to the template petroleum is (2:8) - (5:5);
in the step S2, the temperature of the supermolecule template induced synthesis reaction is 60-80 ℃, the pressure is 40-80MPa, and the time is 1-10h;
in the step S2, the catalysts for the supermolecular template induced synthesis reaction are NiMo/HZSM-5 and NiMo/TiO 2 One of the following;
the template petroleum is paraffinic oil.
2. The process for preparing synthetic petroleum according to claim 1, wherein said catalytic hydrodeoxygenation reaction time is 1-3 hours.
3. The process for preparing synthetic petroleum according to claim 1, wherein said oil raw materials comprise at least two types of oils, said oil raw materials being blended and mixed according to a predetermined synthetic petroleum composition and yield; the oil raw materials comprise a plurality of biomass oil, animal oil, household garbage oil, plastic oil and rubber oil.
4. A production apparatus used in the production process of the synthetic petroleum according to any one of claims 1 to 3, characterized by comprising a raw material catalytic hydrogenation system and a supermolecule synthesis system;
the catalytic hydrogenation system comprises a catalytic hydrogenation reactor, a liquid high-pressure pump and a hydrogen booster pump which are connected with a charging end of the catalytic hydrogenation reactor, and a cooler and a separator which are connected with a discharging end of the catalytic hydrogenation reactor; the supermolecule synthesis system comprises a supermolecule synthesis reactor, a liquid high-pressure pump and a template petroleum high-pressure pump which are connected with the feed end of the supermolecule synthesis reactor, and a separator connected with the discharge end of the supermolecule synthesis reactor.
5. The apparatus of claim 4, further comprising a proportioning and blending system coupled to the liquid high pressure pump of the catalytic hydrogenation system, the proportioning and blending system comprising a proportioning tank and a mixing tank coupled in sequence.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102630247A (en) * | 2009-11-24 | 2012-08-08 | 国际壳牌研究有限公司 | Process for catalytic hydrotreatment of a pyrolysis oil |
| CN102851062A (en) * | 2012-05-08 | 2013-01-02 | 郑州大学 | Organic-solvent-promoted bio-oil catalytic hydrogenation process method |
| CN105925305A (en) * | 2016-04-20 | 2016-09-07 | 神华集团有限责任公司 | Diesel oil and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102630247A (en) * | 2009-11-24 | 2012-08-08 | 国际壳牌研究有限公司 | Process for catalytic hydrotreatment of a pyrolysis oil |
| CN102851062A (en) * | 2012-05-08 | 2013-01-02 | 郑州大学 | Organic-solvent-promoted bio-oil catalytic hydrogenation process method |
| CN105925305A (en) * | 2016-04-20 | 2016-09-07 | 神华集团有限责任公司 | Diesel oil and preparation method thereof |
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