CN107267206B - A kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction - Google Patents

A kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction Download PDF

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Publication number
CN107267206B
CN107267206B CN201710670853.XA CN201710670853A CN107267206B CN 107267206 B CN107267206 B CN 107267206B CN 201710670853 A CN201710670853 A CN 201710670853A CN 107267206 B CN107267206 B CN 107267206B
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reactor
oil
entrance
magnetic ball
catalyst
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CN107267206A (en
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朱爱林
李呈宏
罗明生
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Zhejiang Green Recycling Technology Co., Ltd.
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Taizhou City Green Paul Goods Recycling Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • 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 belongs to the working process technical fields of tire pyrolysis oil, a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction are refered in particular to, including the reaction unit for the modification for feedstock oil being connected in series by the first, second, third reactor；The present invention has the advantage that: simple process, small investment, each index of the cracked oil different fractions product after modification be improved significantly, significantly improve the economic value of tire pyrolysis oil.

Description

A kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction
Technical field
The invention belongs to the working process technical fields of tire pyrolysis oil, and it is mixed to refer in particular to a kind of waste tire cracking vapour bavin wax oil Close the hydrogenation modification method of fraction.
Background technique
Along with the continuous soaring of China's car ownership, the yield of waste tire also rapid growth therewith, according to mesh Preceding waste tire growth rate is up to 20,000,000 tons in the yield estimation of the year two thousand twenty waste tire.However China is useless now The effective rate of utilization of tire is but less than 50%, and therefore, the recovery utilization rate space for improving waste tire is very big.Wherein tire pyrolysis Technology recycles one of the best way as waste tire, and research and application development are rapid.Cracked oil is waste tire The primary product of cracking process, quality directly affect the economic feasibility and development prospect of cracking process.Damaged tire cracking The calorific value of oil is higher, but if it is little using economic value directly as fuel oil, and since wherein sulphur, nitrogen content are high, directly Connecing use will cause serious environmental pollution.Therefore, the outputs stones such as further hydrofinishing desulfurization removing nitric are carried out to cracking oil product Cerebrol, diesel oil and heavy oil component can not only make product using more environmentally-friendly, nonstandard cracking oil product can be more produced as The petrol and diesel oil component of national standard, to greatly promote value-added content of product.
Existing tire pyrolysis technology is usually to distill damaged tire cracked oil first, is fractionated as gasoline fraction, bavin Then oil distillate and heavy oil component carry out hydrotreating for different fractions respectively, so no doubt can be preferably for not With the hydroprocessing scheme of design differentiation the characteristics of fraction, but reaction process process complexity is also resulted in this way, it is required Equipment investment is larger, is not suitable for miniaturization production.For tire pyrolysis oil compared with crude oil, many indexs are all more excellent.Crack oil product Wax content, condensation point are lower than general crude oil, and arene content is higher, and alkane and asphalt content are low, and low-boiling point material is more, flash-point Low, ash content, carbon residue, solid impurity content are seldom.Trace Metals Contents in cracked oil are lower than crude oil, to the later period plus The use of hydrogen catalyst for refining does not impact.Therefore hydro-upgrading processing can directly be carried out to tire pyrolysis oil, this needs It is a kind of to meet the Catalytic processes and operating condition that tire pyrolysis oil mixed fraction is raw material, realize that one step of damaged tire cracked oil adds hydrogen High-grade fuel oil process is generated, thus investment reduction cost.
Summary of the invention
Hydrogen is added to change the object of the present invention is to provide a kind of waste tire of simple process cracking vapour bavin wax oil mixed fraction Matter method.
The object of the present invention is achieved like this:
A kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction, it is characterised in that: including by first, The reaction unit for the modification for feedstock oil that second, third reactor is connected in series, first reactor, second reactor and Specific filling scheme is as follows in three reactors:
The entrance of reaction tube in first reactor to outlet successively loads protective agent 40C, protective agent 40D and magnetic ball, and By the entrance pipe connection in the entrance and first reactor of reaction tube；
The entrance of reaction tube in second reactor to outlet successively loads magnetic ball, catalyst for refining LB207K and magnetic ball, And the entrance pipe in the entrance and second reactor of reaction tube is connected；
The entrance of reaction tube in third reactor to outlet successively loads magnetic ball, catalyst for refining LB207K and magnetic ball, And the entrance of reaction tube is connect with the entrance pipe in third reactor；
Its process flow steps is as follows:
(1) injection is in reaction vessel after feedstock oil being boosted to 12-18MPa by feed pump；
(2) hydrogen is boosted into 15MPa through compressor, then by the hydrogen injection after boosting wait in reaction vessel with liter Feedstock oil mixing after pressure, volume space velocity 0.3-1.0h-1, the volume ratio of hydrogen and feedstock oil is 600-1200Nm3/m3；
(3) it opens nitrogen intake valve nitrogen is passed through in the first, second, third reactor, it will while being passed through nitrogen The temperature of first reactor be heated to 210-320 DEG C, the temperature of second reactor be heated to 300-420 DEG C, third reactor Temperature is heated to 300-420 DEG C；
(4) after step (3) being continued at least 1 hour, nitrogen intake valve is closed, is opened to the ball valve in reaction vessel, it will The feedstock oil mixed in step (2) enters reactor by entrance pipe and starts to react；
Above-mentioned raw materials oil is gasoline, diesel oil and the wax oil mixed fraction of tire pyrolysis oil, the quality of gasoline, diesel oil and wax oil Than for 1:(1.2-3.5): (1.2-3.5).
Above-mentioned raw materials oil is gasoline, diesel oil and the wax oil mixed fraction of tire pyrolysis oil, the quality of gasoline, diesel oil and wax oil When than for 1:2:1.8: feedstock oil boosts to 15MP by feed pump in step (1), feedstock oil injection in reaction vessel into Sample amount is about 0.275kg/h；The volume ratio of hydrogen and feedstock oil in step (2) is 1000Nm3/m3；First in step (3) The temperature of reactor is 250 DEG C, and the temperature of second reactor is 360 DEG C, and the temperature of third reactor is 360 DEG C.
The filling volume that the entrance of reaction tube in above-mentioned first reactor extremely exports the protective agent 40C successively loaded is The filling volume of 200ml, protective agent 40D are 200ml, and the filling volume of magnetic ball is 80ml.
The filling volume that the entrance of reaction tube in the second reactor extremely exports the magnetic ball successively loaded is 130ml, The filling volume of catalyst for refining LB207K is 300ml, and the filling volume of magnetic ball is 80ml.
The filling volume that the entrance of reaction tube in the third reactor extremely exports the magnetic ball successively loaded is 140ml, The filling volume of catalyst for refining LB207K is 300ml, and the filling volume of magnetic ball is 80ml.
Above-mentioned first, second, third reactor inside diameter be 26mm, height 1380mm, thermocouple sheath outer diameter 9.5mm, instead Answering device average cross-section is 381.5mm2。
Above-mentioned first, second, third reactor is by setting 5 tile laser heatings in the heater, every tile height 23cm adds up to high 115cm, and first tile 10cm of reactor inlet distance, the 5th tile is away from reactor outlet 13cm.
Above-mentioned protective agent 40C and protective agent 40D is the substance of nickel molybdenum component, the ratio table of protective agent 40C Area and aperture are all larger than specific surface area and the aperture of protective agent 40D；The catalyst for refining LB207K are as follows: alumina load cobalt The catalyst of molybdenum component, Mo content reaches 10-25w% in catalyst for refining LB207K, and Mo/Co ratio reaches 2-8.
The present invention is prominent and beneficial compared with prior art to be had the technical effect that
The present invention has simple process as a kind of better simply tire pyrolysis oil hydrogenation modification method, and small investment is changed Each index of cracked oil different fractions product after matter be improved significantly, significantly improve the economic value of tire pyrolysis oil.
Detailed description of the invention
Fig. 1 is addition conceptual scheme of the catalyst of the present invention in each reactor.
Fig. 2 be in hydrogenation process of the present invention air speed with the fluctuating change figure of the duration of runs.
Fig. 3 is the density of full distillate oil in hydrogenation process of the present invention with the variation diagram of the duration of runs.
Specific embodiment
With specific embodiment, the invention will be further described with reference to the accompanying drawing, referring to Fig. 1-3:
A kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction, including it is anti-by first, second, third The reaction unit for the modification for feedstock oil for answering device to be connected in series, feedstock oil are gasoline, diesel oil and the wax oil of tire pyrolysis oil Mixed fraction, the mass ratio of gasoline, diesel oil and wax oil are 1:(1.2-3.5): (1.2-3.5), it is preferred that in feedstock oil of the present invention Gasoline, diesel oil and wax oil mass ratio be 1:2:1.8.The internal diameter of first, second, third reactor is 26mm, height 1380mm, thermocouple sheath outer diameter 9.5mm, reactor average cross-section are 381.5mm2, the first, second, third reactor is equal By 5 tile laser heatings in the heater are arranged, the high 23cm of every tile adds up to high 115cm, reactor inlet distance first Piece tile 10cm, the 5th tile is away from reactor outlet 13cm.
Specific filling scheme is as follows in first reactor, second reactor and third reactor:
The entrance of reaction tube in first reactor to outlet successively loads protective agent 40C, protective agent 40D and magnetic ball, instead Should the entrance of pipe extremely to export the filling volume of the protective agent 40C successively loaded be 200ml, the filling volume of protective agent 40D is 200ml, the filling volume of magnetic ball are 80ml；It loads process variable and guarantees inclusion accumulation uniformly, it is more than anti-for preventing the solid of filling After filling, the entrance pipe in the entrance and first reactor of reaction tube is connected for the total height for answering device；
The entrance of reaction tube in second reactor to outlet successively loads magnetic ball, catalyst for refining LB207K and magnetic ball, The filling volume that the entrance of reaction tube extremely exports the magnetic ball successively loaded is 130ml, the filling volume of catalyst for refining LB207K For 300ml, the filling volume of magnetic ball is 80ml；Load process variable guarantee inclusion accumulation uniformly, prevent filling solid be more than The total height of reactor after filling, and the entrance pipe in the entrance and second reactor of reaction tube is connected；
The entrance of reaction tube in third reactor to outlet successively loads magnetic ball, catalyst for refining LB207K and magnetic ball, The filling volume that the entrance of reaction tube extremely exports the magnetic ball successively loaded is 140ml, the filling volume of catalyst for refining LB207K For 300ml, the filling volume of magnetic ball is 80ml；Load process variable guarantee inclusion accumulation uniformly, prevent filling solid be more than The total height of reactor after filling, and the entrance of reaction tube is connect with the entrance pipe in third reactor；
Its process flow steps is as follows:
(1) injection is to which in reaction vessel, the preferred present invention will after feedstock oil being boosted to 12-18MPa by feed pump Feedstock oil boosts to 15MPa, and feedstock oil injection is about 0.275kg/h to the sample volume in reaction vessel；
(2) hydrogen is boosted into 15MPa through compressor, then by the hydrogen injection after boosting wait in reaction vessel with liter The volume ratio of feedstock oil mixing after pressure, hydrogen and feedstock oil is 600-1200Nm3/m3；Preferred hydrogen and raw material of the invention The volume ratio of oil is 1000Nm3/m3。
(3) it opens nitrogen intake valve nitrogen is passed through in the first, second, third reactor, it will while being passed through nitrogen The temperature of first reactor be heated to 210-320 DEG C, the temperature of second reactor be heated to 300-420 DEG C, third reactor Temperature is heated to 300-420 DEG C；The temperature of first reactor is heated to the temperature of 250 DEG C, second reactor by the preferred present invention Degree be heated to 360 DEG C, the temperature of third reactor be heated to 360 DEG C；
(4) after step (3) being continued at least 1 hour, nitrogen intake valve is closed, is opened to the ball valve in reaction vessel, it will The feedstock oil mixed in step (2) enters reactor by entrance pipe and starts to react；Reaction carries out 208 hours in total, reaction A liquids and gases product is collected every 8h after beginning to be analyzed.
Above-mentioned protective agent 40C and protective agent 40D is the substance of nickel molybdenum component, mainly pre-processes and protects The effect of catalyst for refining is protected, wherein the specific surface area of protective agent 40C and aperture are all larger than specific surface area and the hole of protective agent 40D Diameter, facilitates the diffusion of reaction molecular, and have passed through certain presulfurization, and initial activity is higher；Protectant effect mainly has: Particulate matter, dirt, coking, metal impurities etc. in removing or interception feedstock oil, protect major catalyst and extend major catalyst Service life prevents the quick raising of reactor bed pressure drop, extends the operation cycle of device.
Above-mentioned catalyst for refining LB207K are as follows: the catalyst of alumina load cobalt molybdenum component, in catalyst for refining LB207K Mo content reaches 10-25w%, and Mo/Co ratio reaches 2-8.
The composition and property of feedstock oil see the table below in the present invention.
Protective agent 40C and 40D, catalyst for refining LB207K are bought by catalyst producer.
The operating condition of tire pyrolysis oil raw material hydro-upgrading of the present invention is as shown in table 1:
The operational reaction conditions of 1 different kinds of tyre cracked oil raw material hydrofinishing of table
Operate time/h 208
Operating pressure/MPa 15.0
Hydrogen to oil volume ratio/Nm3/m3 1000
Volume space velocity is /h-1 0.5
The mean temperature of reactor one/DEG C 250
The mean temperature of reactor two/DEG C 360
The mean temperature of reactor three/DEG C 360
Further MaterialBalance Computation and product composition is carried out to tire pyrolysis oil hydro-upgrading product to divide with property Analysis, to evaluate the effect of hydro-upgrading Catalytic processes of the present invention.The Catalytic processes of tire pyrolysis oil hydro-upgrading entirety first Process materials balance is as shown in table 2.From Table 2, it can be seen that by hydro-upgrading catalytic process, because being stripped of tire pyrolysis oil In the elements such as most S, N and produce a large amount of H2S、NH3.Furthermore a small amount of hydrocarbon gas product is produced, specific point Son composition is as shown in table 2.Gaseous product other than containing relatively large number of methane, ethane, mainly concentrate by remaining gas product In butylene and C5 +Distribution at most, amounts to the 65w% or more in gaseous product.Product liquid after the hydrogenated modification of feedstock oil In each fraction ratio apparent variation has occurred, wherein diesel oil distillate increased significantly, and reach 68.04%, and wax oil fraction is bright Aobvious to reduce, whole vapour bavin wax oil ratio becomes about 1:3.5:0.4 from original 1:2:1.8.This explanation during hydro-upgrading, Catalytic cracking reaction has occurred in wax oil fraction, so that part wax oil is converted into diesel oil distillate in product.
2 tire pyrolysis oil hydro-upgrading material balance of table
3 hydrofinishing gaseous product of table composition
Product Accounting/w%
Methane 8.64
Ethane 13.8
Ethylene 3.19
Propane 2.68
Propylene 1.95
Iso-butane 2.04
Normal butane 2.69
Butylene 24.72
C5 + 40.29
It is total 100
The composition of the full fraction product liquid of tire pyrolysis oil hydro-upgrading is analyzed with property, result such as table 4 It is shown.As shown in Table 4, after hydro-upgrading, the indexs such as density, viscosity, carbon residue of product liquid obviously become smaller, and liquid produces The H/C atomic ratio of object significantly improves, and illustrates tire pyrolysis oil hydro-upgrading significant effect.
The property of the full fraction product liquid of table 4
In order to compare the variation of product liquid different fractions property respectively, further to the stone brain of hydro-upgrading product liquid Three kinds of oil distillate (IBP~180 DEG C), diesel oil distillate (180~360 DEG C), vacuum distillate (> 360 DEG C) different fractions oils are other It is analyzed, result is as illustrated in tables 5-7.By indices in table 5 it is found that aromatic hydrocarbon content obviously subtracts in naphtha cut It is few, and paraffinicity is significantly improved, the indices such as S, N content have reached higher level.Bavin after hydro-upgrading Oil distillate property is as shown in table 6, and number index big absolutely has reached the quality requirement of national standard light diesel fuel (GB 252-2000), especially It is that the indexs such as sulfur content, acidity have reached higher level.As can be seen from Table 7, the acidity of vacuum distillate, sulphur nitrogen content Etc. indexs reached higher level compared with petrol and diesel oil fraction.
5 hydrotreated naphtha of table (IBP~180 DEG C) property and composition
6 hydrogenated diesel oil fraction of table (180~360 DEG C) property and composition
Table 7 plus hydrogen vacuum distillate (> 360 DEG C) property and composition
Above-described embodiment is only presently preferred embodiments of the present invention, is not limited the scope of the invention according to this, therefore: it is all according to The equivalence changes that structure of the invention, shape, principle are done, should all be covered by within protection scope of the present invention.

Claims (6)

1. a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction, it is characterised in that: including by first, the Two, the reaction unit for the modification for feedstock oil that third reactor is connected in series, first reactor, second reactor and third Specific filling scheme is as follows in reactor:
The entrance of reaction tube in first reactor to outlet successively loads protective agent 40C, protective agent 40D and magnetic ball, and will be anti- It should entrance pipe connection in the entrance and first reactor of pipe；
The entrance of reaction tube in second reactor to outlet successively loads magnetic ball, catalyst for refining LB207K and magnetic ball, and will Entrance pipe connection in the entrance and second reactor of reaction tube；
The entrance of reaction tube in third reactor to outlet successively loads magnetic ball, catalyst for refining LB207K and magnetic ball, and will The entrance of reaction tube is connect with the entrance pipe in third reactor；
The protective agent 40C and protective agent 40D is the substance of nickel molybdenum component, the specific surface area of protective agent 40C Specific surface area and the aperture of protective agent 40D are all larger than with aperture；The catalyst for refining LB207K is alumina load cobalt molybdenum group Point catalyst, Mo content is 10-25w% in catalyst for refining LB207K, and Mo/Co value is 2-8；
Its process flow steps is as follows:
(1) injection is in reaction vessel after feedstock oil being boosted to 12-18MPa by feed pump；
(2) hydrogen is boosted into 15MPa through compressor, then by the hydrogen injection after boosting after in reaction vessel and after boosting Feedstock oil mixing, volume space velocity 0.3-1.0h-1, the volume ratio of hydrogen and feedstock oil is 600-1200Nm3/m3；
(3) it opens nitrogen intake valve nitrogen is passed through in the first, second, third reactor, by first while being passed through nitrogen The temperature of reactor be heated to 210-320 DEG C, the temperature of second reactor be heated to the temperature of 300-420 DEG C, third reactor It is heated to 300-420 DEG C；
(4) after step (3) being continued at least 1 hour, nitrogen intake valve is closed, is opened to the ball valve in reaction vessel, by step (2) feedstock oil mixed in enters reactor by entrance pipe and starts to react.
2. a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction according to claim 1, special Sign is: the feedstock oil is gasoline, diesel oil and the wax oil mixed fraction of tire pyrolysis oil, the quality of gasoline, diesel oil and wax oil Than for 1:(1.2-3.5): (1.2-3.5).
3. a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction according to claim 2, special Sign is: the feedstock oil is gasoline, diesel oil and the wax oil mixed fraction of tire pyrolysis oil, the quality of gasoline, diesel oil and wax oil When than for 1:2:1.8: feedstock oil boosts to 15MP by feed pump in step (1), feedstock oil injection in reaction vessel into Sample amount is 0.275kg/h；The volume ratio of hydrogen and feedstock oil in step (2) is 1000Nm3/m3；First in step (3) is anti- The temperature for answering device is 250 DEG C, and the temperature of second reactor is 360 DEG C, and the temperature of third reactor is 360 DEG C.
4. a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction according to claim 1, special Sign is:
The filling volume that the entrance of reaction tube in the first reactor extremely exports the protective agent 40C successively loaded is 200ml, The filling volume of protective agent 40D is 200ml, and the filling volume of magnetic ball is 80ml；
The filling volume that the entrance of reaction tube in the second reactor extremely exports the magnetic ball successively loaded is 130ml, purification The filling volume of catalyst LB207K is 300ml, and the filling volume of magnetic ball is 80ml；
The filling volume that the entrance of reaction tube in the third reactor extremely exports the magnetic ball successively loaded is 140ml, purification The filling volume of catalyst LB207K is 300ml, and the filling volume of magnetic ball is 80ml.
5. a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction according to claim 4, special Sign is: the internal diameter of first, second, third reactor be 26mm, height 1380mm, thermocouple sheath outer diameter 9.5mm, instead Answering device average cross-section is 381.5mm2。
6. a kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction according to claim 4, special Sign is: first, second, third reactor is by setting 5 tile laser heatings in the heater, every tile height 23cm adds up to high 115cm, and first tile 10cm of reactor inlet distance, the 5th tile is away from reactor outlet 13cm.
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