CN105950213A - Environment-friendly solvent and partial monomer alkane production device and use method thereof - Google Patents
Environment-friendly solvent and partial monomer alkane production device and use method thereof Download PDFInfo
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0409—Extraction of unsaturated hydrocarbons
- C10G67/0418—The hydrotreatment being a hydrorefining
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0409—Extraction of unsaturated hydrocarbons
- C10G67/0436—The hydrotreatment being an aromatic saturation
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/883—Molybdenum and nickel
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- 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
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- 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
- C10G2400/06—Gasoil
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
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- 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
- C10G2400/18—Solvents
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Abstract
The invention provides an environment-friendly solvent and partial monomer alkane production device and a use method thereof. The invention adopts the technical scheme that the environment-friendly solvent and partial monomer alkane production device mainly comprises a feed pump (1), a heat exchanger unit (2), a circulating hydrogen compressor (3), a new hydrogen line (4), a light hydrocarbon removal tower (5), a heating furnace (6), a pre-hydrogenating reactor (7), a main hydrogenating reactor (8), an absorption reactor (9), a first dearomatization reactor (10), a second dearomatization reactor (11), a high-pressure separator (12), a low-pressure separator (13), a pentane rectifying tower (14), a hexane rectifying tower (15), a heptane rectifying tower I (16), a heptane rectifying tower II (17), a hydrogenation tail oil rectifying tower (18), an isohexane rectifying tower (19), an N-hexane extraction and rectification tower (20), a first extraction solvent recovery tower (21), a methyl cyclopentane rectifying tower (22), a second extraction solvent recovery tower (23), a benzene rectifying tower (24), a first extraction solvent regeneration evaporator (25) and a second extraction solvent regeneration evaporator (26). The environment-friendly solvent and partial monomer alkane production device provided by the invention is reasonable and practical in design and better in economic benefits.
Description
Technical field:
The present invention relates to solvent naphtha technical field, especially a kind of environmentally friendly solvent and partial monosomy alkane process units and use thereof
Method.
Background technology:
China's existing petroleum hydrocarbon solvent process units and method generally are directed to raw material sources and product standard at that time and carry out
Design, so existence processes raw material limited, product quality poor (Volatile organic emissions is high, and abnormal smells from the patient is big), device processing spirit
The problems such as poor activity, can not meet the demand for development of current environmentally friendly solvent.Petroleum hydrocarbon solvent production technology the most both at home and abroad
Mainly having extraction fractional distillation, adsorption method of separation, sulfonation method and catalytic hydrogenation method, wherein catalytic hydrogenation method is most widely used
Method.Catalytic hydrogenation method solvent naphtha produces and includes cut and refined two processes.Catalytic hydrogenation plant investment is bigger, expensive
Metallic catalyst is expensive, is not suitable for medium-sized and small enterprises investment construction.Sulfonation method is restricted because of the waste pollution environment of generation.Institute
Urgently to research and develop new preparation facilities and production method, play low pressure hydrofining and produce high-end solvent product with solvent extraction
The comprehensive advantage of product, to meet the application needs of environmentally friendly solvent, solves current China and is short of high-end high-purity environmentally friendly solvent the most in a large number
Problem.Hydrofinishing method mainly depends on the consideration of device operation pressure, temperature and catalyst input cost at present.Urge in guarantee
On the premise of the selectivity of agent, select low-valent metal catalyst can be substantially reduced catalyst cost, can reduce anti-simultaneously
Answer pressure and reaction temperature, reduce hydrogen consumption.Inevitable the combining with rectification of hydrofinishing just can obtain high purity product.Conventional distillation method
Can not get high-purity monomer alkane product；Molecular sieve adsorption is the most saturated, regeneration difficulty；Extraction fractional distillation is possible not only to obtain relatively
Highly purified product, production cost is relatively low simultaneously, is usually used in aromatic hydrocarbons and separates with non-aromatics.Extract for extraction fractional distillation
The selection taking solvent is extremely important, and the extractant that we commonly use includes N-Methyl pyrrolidone, glycols, sulfolane, dimethyl
Sulfoxide, N-formyl-morpholine etc..The mass ratio (solvent ratio) of extractant and raw material is to the relative volatility between feed change component
Have a major impact；Extractant has a major impact for extraction efficiency with the mass transfer area of raw material.In certain opereating specification, solvent
Ratio is the biggest, and the effect of extract and separate is the best, but with the increase of solvent ratio, the consumption of extractant can increase, and causes energy consumption and one-tenth
This increase.By using new packing extraction tower to increase extraction tower inner transmission matter area, improve extraction efficiency, effectively reduce because of molten
Agent is than increasing the solvent consumption caused.Therefore, the selection of catalyst, the process technique of extractant and extraction tower design device
Operating cost and efficiency have a major impact.
Summary of the invention
It is an object of the invention to overcome above-mentioned deficiency, it is provided that a kind of environmentally friendly solvent and partial monosomy alkane combined production device,
Particularly to pentane, normal hexane, hexane, petroleum ether, heptane, benzene, dimethylbenzene and state V light oil constituents from extractant in process
Circulation and refined a kind of environmentally friendly solvent and partial monosomy alkane process units and using method thereof, its technical scheme is: charging
Pump, heat exchanger package, de-lighter hydrocarbons tower are sequentially connected and connect, and new hydrogen line one end connects de-lighter hydrocarbons tower, and the other end connects circulating hydrogen compressor,
Heating furnace one side lower part connects de-lighter hydrocarbons tower, and opposite side top connects pre-hydrogenator, the pre-hydrotreating reaction of reactor unit
Device, main hydrogenation reactor, adsorptive reactor, first take off arylation reaction device, second take off arylation reaction device and be sequentially connected and connect, high-pressure separator
Side connects heat exchanger package, and top connects circulating hydrogen compressor, and bottom connects low pressure separator, and main hydrogenation reactor, low pressure are divided
From device and the pentane rectifying column of rectification cell, hexane rectifying column, heptane rectifying column one, heptane rectifying column two, hydrogenation tail oil rectification
Tower is sequentially connected and connects, the isohexane rectifying column of the pentane rectifying column bottom outlet of rectification cell two and rectification extraction cells, just
Hexane extractive distillation column, the first extractant recovery tower, methyl cyclopentane rectifying column, the second extractant recovery tower, benzene rectifying column depend on
Secondary being connected, the first extractant recovery tower and the second extractant recovery tower are respectively equipped with the first extractant regeneration vaporizer and second
Extractant regeneration vaporizer, n-hexane extraction rectifying column, the first extractant recovery tower and the first extractant regeneration vaporizer are formed
Loop, methyl cyclopentane rectifying column, the second extractant recovery tower and the second extractant regeneration vaporizer form loop.
With boiling range naphtha cut between 30-280 DEG C as raw material, enter de-after raw material is pumped into heat exchanger package heat exchange
Lighter hydrocarbons tower, the material removing light component mixes with hydrogen, pumps into after heating furnace heats up and carries out secondary hydrogenation, suction through reactor unit
Attached, secondary takes off arylation reaction, and reactant enters high-pressure separator, circulates again through compressor through the isolated hydrogen of high-pressure separator
Utilizing, the material after dehydrogenation enters rectification cell or rectification extraction cells through low pressure separator, carries out phase according to product boiling range
The cutting rectification answered can get environmentally friendly solvent product and part high-purity monomer alkane, through rectification cell, can obtain pentane foaming agent, with
Hexane, heptane are each trade mark environmentally friendly solvent and petroleum ether, the high boiling point lightweight white oil solvent of main component, and hydrogenation tail oil is through rectification
Can obtain state V light oil, the material entering rectification extraction cells can obtain high-purity normal hexane, isohexane, methyl ring penta through rectification, extraction
Alkane, benzene, xylene solvent.Reactor unit uses the de-virtue catalysis of high selectivity bimetallic catalyst, high-efficiency adsorbent and the degree of depth
Agent；Raw material and product carry out heat exchange, improve device comprehensive utilization of energy rate, rectification and rectification extraction cells and use novel filling out
Material tower, and be ranked up by overhead product volatility；Use pinch analysis method synthesis heat-exchange network and carry out heat exchanger layout.Excellent
Select the dual element guard catalyst of aluminum silicon, molybdenum nickel, be mainly used in improving fluid distrbution, trapping impurity, reducing reactor pressure decrease, with
Time saturation of olefins, aluminum silicon protective agent: profile is five-pointed star ring φ 19.0mm*19.0mm, and bulk density is 800-860Kg/m3, crushing
Intensity >=102N/cm；Molybdenum nickel protective agent: profile is gear ring φ 10.0mm*10.0mm, bulk density is 800-830Kg/m3,
Crushing strength >=30N/cm, is placed in hydrogenation reactor on hydrogenation catalyst according to the order that diameter is up big and down small.Excellent
The bimetallic hydrogenation denitrating catalyst selecting active metal to be molybdenum nickel, its active center is metal molybdenum, nickel, and profile is Herba Trifolii Pratentis, La Xi
Ring φ 1.6mm*1.6mm, φ 6.0mm*6.0mm, bulk density is 500-660Kg/m3, specific surface area is 100 140cm2/ kg,
Crushing strength >=120N/cm, is placed in hydrogenation reactor under guard catalyst according to the order that diameter is up big and down small.Excellent
The adsorption catalyst of activity ZnO, MgO, CaO accelerator is added in choosing, is mainly used in adsorbing chlorine, H2S and trace metal impurities, permissible
Avoiding the hydrogen sulfide in recycle hydrogen to cause catalyst poisoning to inactivate, improve catalyst activity stability, bulk density is 650-
750Kg/m3, crushing strength >=50N/cm, work chlorosity (Wt) >=30.0%.Preferably there is the nickel system catalysis of high hydrogenation dearomatization activity
Agent, its active center is metallic nickel, and profile is spherical φ 2.0-4.0mm*2.0-4.0mm, and bulk density is 800-820Kg/m3,
Crushing strength ＞ 90N/cm, pore volume ＞ 0.3cm3/ 100g, two de-arylation reaction devices are loaded by the mass ratio of front and back 7:13.
Enter de-lighter hydrocarbons tower after boiling range naphtha cut between 30-280 DEG C is pumped into heat exchanger package heat exchange, remove the thing of light component
Material mixes with hydrogen, carries out secondary hydrogenation through reactor unit, absorption, secondary take off arylation reaction, through changing after pumping into heating furnace intensification
After heat, reactant enters high-pressure separator, after gas-liquid separation, hydrogen through compressor circulation again with, material after dehydrogenation is through slow
Rushing tank and enter low pressure separator, isolate dissolved hydrogen and other gas phase enters device dry gas pipe network, liquid phase enters rectification cell or essence
Evaporate extraction cells.Pre-hydrogenator operating condition: pressure is 1.4-1.8Mp, inlet temperature is 135-170 DEG C, outlet temperature
For 185-210 DEG C, hydrogen-oil ratio 1:200, air speed is 5.0-7.0h-1.Strict control pre-hydrogenator temperature, prevents alkene certainly
Poly-, main hydrogenation reactor operating condition: pressure is 2.3-4.8Mp, inlet temperature is 220-240 DEG C, and outlet temperature is 270-290
DEG C, hydrogen-oil ratio 1:200, air speed is 0.25h-1, adsorptive reactor operating condition: air speed is 0.5-3.5 h-1, temperature is 180-
400 DEG C, pressure is normal pressure-4.8 Mp, and first takes off arylation reaction device (10) operating condition: pressure is 1.0-1.5Mp, and inlet temperature is
120-160 DEG C, outlet temperature is 150-190 DEG C, and air speed is 0.75h-1, second takes off arylation reaction device (11) operating condition: pressure is
1.0-1.5Mp, inlet temperature is 125-175 DEG C, and outlet temperature is 160-210 DEG C, and air speed is 0.75h-1, high-pressure separator operates
Pressure is 2.0Mp.Two adsorptive reactors are set, during operation one open one standby, ZnO, MgO, CaO adsorption catalyst exchange in turn or
Use by proportioning, it is simple to not parking more catalyst changeout.
Rectifying column tower bottom reboiler thermal source uses 1.2Mpa, 220 DEG C of conduction oils, and wherein taking off lighter hydrocarbons column overhead temperatures is
43.5-52 DEG C, column bottom temperature be 60-71 DEG C, operation pressure be 0.5Mpa, the light component of removing below C4.
Extractant recovery tower forms loop with extractant regeneration vaporizer, can effectively be removed by extractant regeneration vaporizer
Extractant impurity, improves extractant cyclic utilization rate, extends service life of extractant, reduces Solvent quantity.For improving heat exchange
Efficiency and the degree of depth, effectively reduce extractant backflow pressure drop, and extract return method column overhead condenser, overhead product cooler use ripple
Managing reverse-flow steel alloy heat exchanger, cooling medium uses ethylene glycol；Remaining overhead condenser, overhead product cooler cooling medium
Use cold water.
Beneficial effects of the present invention: practicality reasonable in design, hydrogen consumption, energy consumption are low, and operation pressure is low, and rectification purity is high, the three wastes
Discharge is few, technological operation simple and flexible, and product is in addition to state V light oil, and low sulfur and low aromatics, purity is high, adapts to current environmentally friendly solvent former
Material is uncertain strong, the diversified requirement of the market demand, better economic benefit.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention；
Fig. 2 is raw oil character schematic diagram of the present invention；
Fig. 3 is embodiment of the present invention schematic diagram.
Detailed description of the invention
As it is shown in figure 1, a kind of environmentally friendly solvent and partial monosomy alkane process units and using method thereof, mainly by feed pump
1, heat exchanger package 2, circulating hydrogen compressor 3, new hydrogen line 4, de-lighter hydrocarbons tower 5, heating furnace 6, pre-hydrogenator 7, main hydrogenation reaction
Device 8, adsorptive reactor 9, first take off arylation reaction device 10, second take off arylation reaction device 11, high-pressure separator 12, low pressure separator 13,
Pentane rectifying column 14, hexane rectifying column 15, heptane rectifying column 1, heptane rectifying column 2 17, hydrogenation tail oil rectifying column 18, dissident
Alkane rectification tower 19, n-hexane extraction rectifying column the 20, first extractant recovery tower 21, methyl cyclopentane rectifying column 22, second extract
Agent recovery tower 23, benzene rectifying column the 24, first extractant regeneration vaporizer 25 and the second extractant regeneration vaporizer 26 are constituted；Charging
Pump 1, heat exchanger package 2, de-lighter hydrocarbons tower 5 are sequentially connected and connect, and new hydrogen line 4 one end connects de-lighter hydrocarbons tower 5, and the other end connects circulation hydrogen pressure
Contracting machine 3, heating furnace 6 one side lower part connects de-lighter hydrocarbons tower 5, and opposite side top connects pre-hydrogenator 7, reactor unit pre-
Hydrogenation reactor 7, main hydrogenation reactor 8, adsorptive reactor 9, first take off arylation reaction device 10, second take off arylation reaction device 11 phase successively
Connecting, high-pressure separator 12 side connects heat exchanger package 2, and top connects circulating hydrogen compressor 3, and bottom connects low pressure separator
13, main hydrogenation reactor 8, low pressure separator 9 and the pentane rectifying column 14 of rectification cell, hexane rectifying column 15, heptane rectifying column
One 16, heptane rectifying column 2 17, hydrogenation tail oil rectifying column 18 are sequentially connected and connect, and pentane rectifying column 14 bottoms of rectification cell goes out
Mouth two and the isohexane rectifying column 19 of rectification extraction cells, n-hexane extraction rectifying column the 20, first extractant recovery tower 21, methyl
Pentamethylene. rectifying column the 22, second extractant recovery tower 23, benzene rectifying column 24 are sequentially connected and connect, the first extractant recovery tower 21 and
Two extractant recovery towers 23 are respectively equipped with the first extractant regeneration vaporizer 25 and the second extractant regeneration vaporizer 26, normal hexane
Extractive distillation column the 20, first extractant recovery tower 21 and the first extractant regeneration vaporizer 25 form loop, methyl cyclopentane essence
Evaporate tower the 22, second extractant recovery tower 23 and the second extractant regeneration vaporizer 26 forms loop.
Present invention process flow process: first carry out alkali cleaning pretreatment according to naphtha cut feedstock property, contains sulfur in raw material
Amount is down to below 2500ppm.Raw material is entered after feed pump 1 pumps into heat exchanger package 2 heat exchange de-lighter hydrocarbons tower 5, removes light component
Material before heating furnace 6, carried out new hydrogen with circulating hydrogen compressor 3 recycle hydrogen with new hydrogen line 4 mixed, enter after heating furnace 6 heats up and depend on
The secondary pre-hydrogenator 7 through reactor unit, main hydrogenation reactor 8, adsorptive reactor 9, first take off arylation reaction device 10,
Two take off that arylation reaction device 11 carries out secondary hydrogenation, absorption, secondary take off arylation reaction, enter high pressure and divide after reactant heat exchanger package 2 heat exchange
From device 12, isolated hydrogen compresses through circulating hydrogen compressor 3 and again recycles, and the material after dehydrogenation is through low pressure separator
13 enter rectification cell or rectification extraction cells, cut rectification accordingly according to product boiling range and can get environmentally friendly solvent product
And part high-purity monomer alkane.Through rectification cell, pentane foaming agent can be obtained, each trade mark ring with hexane, heptane as main component
Protecting solvent and petroleum ether, lightweight white oil etc., hydrogenation tail oil can obtain high boiling solvent and state V light oil through rectification.Entrance rectification extracts
The material of unit can obtain high-purity normal hexane, isohexane, methyl cyclopentane, benzene, dimethylbenzene equal solvent through rectification, extraction.
Five-pointed star ring aluminum silicon protective agent preferable particle size 19.0mm in pre-hydrogenator 7, the gear ring nickel preferred grain of molybdenum protective agent
Footpath 10.0mm, Raschig ring nickel molybdenum catalyst preferable particle size 6.0mm, the preferential particle diameter of reactor bottom is 6.0mm Yu 13.0mm porcelain ball
Backing supports.The porcelain ball of the catalyst of three kinds of shapes and two kinds of particle diameters preferentially presses the volume of 4:8:73:3:3 by order described above
Ratio loads.
Five-pointed star ring aluminum silicon protective agent preferable particle size 19.0mm in main hydrogenation reactor 8, the gear ring nickel preferred grain of molybdenum protective agent
Footpath 10.0mm, Raschig ring nickel molybdenum catalyst preferable particle size 6.0mm, Herba Trifolii Pratentis nickel molybdenum catalyst preferable particle size 1.6mm, at the bottom of reactor
The preferential particle diameter in portion is that 3.0mm, 6.0mm support with 13.0mm porcelain ball backing.The catalyst of four kinds of shapes and the porcelain ball of three kinds of particle diameters
Preferentially load by the volume ratio of 4:4:12:75:3:3:3 by order described above.
First takes off preferential porcelain ball particle diameter 13.0mm, 6.0mm porcelain ball, the preferential particle diameter of spherical dearomatization catalyst in arylation reaction device 10
2-4mm, preferential porcelain ball particle diameter 6.0mm, preferential porcelain ball particle diameter 6.0mm, spherical dearomatization catalyst preferential particle diameter 2-4mm, preferential porcelain
Spherolite footpath 6.0mm, preferential porcelain ball particle diameter 13.0mm.Catalyst and porcelain ball preferentially press 3:2:22:2:2:22 by order described above:
The volume ratio of 2:2 is loaded.
Second takes off preferential porcelain ball particle diameter 13.0mm, 6.0mm porcelain ball, the preferential particle diameter of spherical dearomatization catalyst in arylation reaction device 11
2-4mm, preferential porcelain ball particle diameter 6.0mm, preferential porcelain ball particle diameter 6.0mm, spherical dearomatization catalyst preferential particle diameter 2-4mm, preferential porcelain
Spherolite footpath 6.0mm, preferential porcelain ball particle diameter 13.0mm.Catalyst and porcelain ball preferentially press 3:2:34:2:2:34 by order described above:
The volume ratio of 2:2 is loaded.
Raw oil character (see figure 2) of the present invention.
Embodiment 1(is shown in Fig. 3)
Entering de-lighter hydrocarbons tower after raw material A pumps into heat exchanger package heat exchange, heated stove is warmed up to 135 DEG C of entrance reaction members to be carried out
Deep hydrodesulfurizationof reaction, denitrogenation, dechlorination reaction and de-virtue saturated reaction；Product is entered height and is added separator gas-liquid separation,
The hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters distillation system through low pressure separator, isolates each and evaporates
The solvent naphtha product of segmentation.Through rectification cell, go out pentane foaming agent product and 30-60 DEG C of petroleum ether product in pentane rectifying column rectification
Product；The 6# plant extraction solvent with hexane as main component and 60-90 DEG C of petroleum ether product is gone out in hexane rectifying column rectification；In heptan
Alkane rectification tower one rectification goes out the 120# rubber industry solvent with heptane as main component and 90-120 DEG C of petroleum ether product；In heptan
Alkane rectification tower two rectification goes out 120-160 DEG C of W2-20 lightweight white oil；Tail oil hydrogenated tail oil rectifying column rectification can obtain state V light oil.
In addition to state V light oil, products obtained therefrom is without sulfur, and arene content is extremely low, meets that environmentally friendly solvent abnormal smells from the patient is little, Volatile organic emissions is low
Requirement.
Embodiment 2(is shown in Fig. 3)
Entering de-lighter hydrocarbons tower after raw material B pumps into heat exchanger package heat exchange, heated stove is warmed up to 145 DEG C of entrance reaction members to be carried out
Deep hydrodesulfurizationof reaction, denitrogenation, dechlorination reaction and de-virtue saturated reaction；Product is entered height and is added separator gas-liquid separation,
The hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters distillation system through low pressure separator, isolates each and evaporates
The solvent naphtha product of segmentation.Through rectification cell, go out pentane foaming agent product and 30-60 DEG C of petroleum ether product in pentane rectifying column rectification
Product；The 6# plant extraction solvent with hexane as main component and 60-90 DEG C of petroleum ether product is gone out in hexane rectifying column rectification；In heptan
Alkane rectification tower one rectification goes out the 120# rubber industry solvent with heptane as main component and 90-120 DEG C of petroleum ether product；In heptan
Alkane rectification tower two rectification goes out 20# paint industry solvent and 120-160 DEG C of W2-20 lightweight white oil；135-170 DEG C of W2-30 lightweight
White oil, 155-200 DEG C of W2-40 lightweight white oil, 185-225 DEG C of W2-60 lightweight white oil, 195-235 DEG C of W2-70 lightweight white oil,
The high boiling points such as 205-245 DEG C of W2-80 lightweight white oil, 215-255 DEG C of W2-90 lightweight white oil, 230-270 DEG C of W2-100 lightweight white oil
Solvent, hydrogenation tail oil can obtain state V light oil through rectification.In addition to state V light oil, products obtained therefrom is without sulfur, and arene content is extremely low, meets ring
Protect the requirement that solvent odor is little, Volatile organic emissions is low.
Embodiment (see figure 3)
Directly mixing with hydrogen without de-lighter hydrocarbons tower after raw material C is pumped into heat exchanger package heat exchange, heated stove is warmed up to 125 DEG C of entrance
Reaction member carries out deep hydrodesulfurizationof reaction, denitrogenation, dechlorination reaction and de-virtue saturated reaction；Product is entered height and is added separation
Device gas-liquid separation, the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters distillation system through low pressure separator, point
Separate out the solvent naphtha product of each fraction section.Through rectification cell, go out pentane foaming agent product and 30-60 in pentane rectifying column rectification
DEG C petroleum ether product；The 6# plant extraction solvent with hexane as main component and 60-90 DEG C of oil is gone out in hexane rectifying column rectification
Ether product；The 120# rubber industry solvent with heptane as main component and 90-120 DEG C of oil is gone out in heptane rectifying column one rectification
Ether product；120-160 DEG C of W2-20 lightweight white oil is gone out in heptane rectifying column two rectification；Tail oil hydrogenated tail oil rectifying column rectification can
Obtain state V light oil.In addition to state V light oil, products obtained therefrom is without sulfur, and arene content is extremely low, meets that environmentally friendly solvent abnormal smells from the patient is little, volatility has
The requirement that the discharge of machine thing is low.
Embodiment 4(is shown in Fig. 3)
Directly mixing with hydrogen without de-lighter hydrocarbons tower after raw material D is pumped into heat exchanger package heat exchange, heated stove is warmed up to 155 DEG C of entrance
Reaction member carries out deep hydrodesulfurizationof reaction, denitrogenation, dechlorination reaction and de-virtue saturated reaction；Product is entered height and is added separation
Device gas-liquid separation, the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters distillation system through low pressure separator, point
Separate out the solvent naphtha product of each fraction section.Through rectification cell, go out pentane foaming agent product and 30-60 in pentane rectifying column rectification
DEG C petroleum ether product；The 6# plant extraction solvent with hexane as main component and 60-90 DEG C of oil is gone out in hexane rectifying column rectification
Ether product；The 120# rubber industry solvent with heptane as main component and 90-120 DEG C of oil is gone out in heptane rectifying column one rectification
Ether product；120-160 DEG C of W2-20 lightweight white oil is gone out in heptane rectifying column two rectification；Tail oil hydrogenated tail oil rectifying column rectification can
Obtain state V light oil.In addition to state V light oil, products obtained therefrom is without sulfur, and arene content is extremely low, meets that environmentally friendly solvent abnormal smells from the patient is little, volatility has
The requirement that the discharge of machine thing is low.
Embodiment 5
Above example gained 6# plant extraction solvent fraction is pumped into rectification extraction cells, extracts through rectification, isohexane, first can be obtained
The products such as cyclopentane, mixed xylenes and high-purity normal hexane, benzene.Gained normal hexane product purity is up to more than 99%, and other produces
Product are without sulfur, and arene content is extremely low, meet the requirement that environmentally friendly solvent abnormal smells from the patient is little, Volatile organic emissions is low.
Claims (10)
1. an environmentally friendly solvent and partial monosomy alkane process units and using method thereof, it is characterised in that: feed pump (1), change
Hot device group (2), de-lighter hydrocarbons tower (5) are sequentially connected and connect, and new hydrogen line (4) one end connects de-lighter hydrocarbons tower (5), and the other end connects recycle hydrogen
Compressor (3), heating furnace (6) side lower part connects de-lighter hydrocarbons tower (5), and opposite side top connects pre-hydrogenator (7), reaction
The pre-hydrogenator (7) of device unit, main hydrogenation reactor (8), adsorptive reactor (9), first take off arylation reaction device (10), second
De-arylation reaction device (11) is sequentially connected and connects, and high-pressure separator (12) side connects heat exchanger package (2), and top connects recycle hydrogen compression
Machine (3), bottom connects low pressure separator (13), and main hydrogenation reactor (8), low pressure separator (9) are smart with the pentane of rectification cell
Evaporate tower (14), hexane rectifying column (15), heptane rectifying column one (16), heptane rectifying column two (17), hydrogenation tail oil rectifying column (18)
It is sequentially connected and connects, pentane rectifying column (14) bottom outlet two of rectification cell and the isohexane rectifying column of rectification extraction cells
(19), n-hexane extraction rectifying column (20), the first extractant recovery tower (21), methyl cyclopentane rectifying column (22), the second extraction
Agent recovery tower (23), benzene rectifying column (24) are sequentially connected and connect, the first extractant recovery tower (21) and the second extractant recovery tower
(23) the first extractant regeneration vaporizer (25) and the second extractant regeneration vaporizer (26), n-hexane extraction rectification it are respectively equipped with
Tower (20), the first extractant recovery tower (21) form loop, methyl cyclopentane rectification with the first extractant regeneration vaporizer (25)
Tower (22), the second extractant recovery tower (23) form loop with the second extractant regeneration vaporizer (26).
A kind of environmentally friendly solvent the most according to claim 1 and partial monosomy alkane process units and using method thereof, it is special
Levy and be: with boiling range naphtha cut between 30-280 DEG C as raw material, enter de-after raw material is pumped into heat exchanger package heat exchange
Lighter hydrocarbons tower, the material removing light component mixes with hydrogen, pumps into after heating furnace heats up and carries out secondary hydrogenation, suction through reactor unit
Attached, secondary takes off arylation reaction, and reactant enters high-pressure separator, circulates again through compressor through the isolated hydrogen of high-pressure separator
Utilizing, the material after dehydrogenation enters rectification cell or rectification extraction cells through low pressure separator, carries out phase according to product boiling range
The cutting rectification answered can get environmentally friendly solvent product and part high-purity monomer alkane, through rectification cell, can obtain pentane foaming agent, with
Hexane, heptane are each trade mark environmentally friendly solvent and petroleum ether, the high boiling point lightweight white oil solvent of main component, and hydrogenation tail oil is through rectification
Can obtain state V light oil, the material entering rectification extraction cells can obtain high-purity normal hexane, isohexane, methyl ring penta through rectification, extraction
Alkane, benzene, xylene solvent.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
It is characterised by: reactor unit uses high selectivity bimetallic catalyst, high-efficiency adsorbent and degree of depth dearomatization catalyst；Raw material with
Product carries out heat exchange, improves device comprehensive utilization of energy rate, rectification and rectification extraction cells and uses novel packed tower, and presses
Overhead product volatility is ranked up；Use pinch analysis method synthesis heat-exchange network and carry out heat exchanger layout.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
It is characterised by: preferably aluminum silicon, the dual element guard catalyst of molybdenum nickel, is mainly used in improving fluid distrbution, trapping impurity, reducing instead
Answer device pressure drop, simultaneously saturation of olefins, aluminum silicon protective agent: profile is five-pointed star ring φ 19.0mm*19.0mm, and bulk density is 800-
860Kg/m3, crushing strength >=102N/cm；Molybdenum nickel protective agent: profile is gear ring φ 10.0mm*10.0mm, and bulk density is
800-830Kg/m3, crushing strength >=30N/cm, it is placed in hydrogenation reactor hydrogenation according to the order that diameter is up big and down small
On catalyst.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
It is characterised by: preferably active metal is the bimetallic hydrogenation denitrating catalyst of molybdenum nickel, and its active center is metal molybdenum, nickel, and profile is
Herba Trifolii Pratentis, Raschig ring φ 1.6mm*1.6mm, φ 6.0mm*6.0mm, bulk density is 500-660Kg/m3, specific surface area is
100—140cm2/ kg, crushing strength >=120N/cm, be placed in hydrogenation reactor guarantor according to the order that diameter is up big and down small
Protect under catalyst.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
It is characterised by: preferably add the adsorption catalyst of activity ZnO, MgO, CaO accelerator, is mainly used in adsorbing chlorine, H2S and trace gold
Belong to impurity, the hydrogen sulfide in recycle hydrogen can be avoided to cause catalyst poisoning to inactivate, improve catalyst activity stability, pile up close
Degree is 650-750Kg/m3, crushing strength >=50N/cm, work chlorosity (Wt) >=30.0%.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
It is characterised by: preferably having the nickel catalyst of high hydrogenation dearomatization activity, its active center is metallic nickel, and profile is spherical φ 2.0-
4.0mm*2.0-4.0mm, bulk density is 800-820Kg/m3, crushing strength ＞ 90N/cm, pore volume ＞ 0.3cm3/ 100g, two
De-arylation reaction device is loaded by the mass ratio of front and back 7:13.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
It is characterised by: after boiling range naphtha cut between 30-280 DEG C is pumped into heat exchanger package heat exchange, enter de-lighter hydrocarbons tower, removing
The material of light component mixes with hydrogen, pumps into and carries out secondary hydrogenation, absorption, the de-virtue of secondary through reactor unit after heating furnace heats up
Reaction, after heat exchange reactant enter high-pressure separator, after gas-liquid separation, hydrogen through compressor circulation again with, after dehydrogenation
The buffered tank of material enter low pressure separator, isolate dissolved hydrogen and other gas phase enter device dry gas pipe network, liquid phase enters essence
Evaporate unit or rectification extraction cells.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof, its
Being characterised by: pre-hydrogenator operating condition: pressure is 1.4-1.8Mp, inlet temperature is 135-170 DEG C, and outlet temperature is
185-210 DEG C, hydrogen-oil ratio 1:200, air speed is 5.0-7.0h-1, strict control pre-hydrogenator temperature, prevent alkene autohemagglutination,
Main hydrogenation reactor operating condition: pressure is 2.3-4.8Mp, inlet temperature is 220-240 DEG C, and outlet temperature is 270-290 DEG C,
Hydrogen-oil ratio 1:200, air speed is 0.25h-1, adsorptive reactor operating condition: air speed is 0.5-3.5 h-1, temperature is 180-400
DEG C, pressure is normal pressure-4.8 Mp, and first takes off arylation reaction device (10) operating condition: pressure is 1.0-1.5Mp, and inlet temperature is
120-160 DEG C, outlet temperature is 150-190 DEG C, and air speed is 0.75h-1, second takes off arylation reaction device (11) operating condition: pressure is
1.0-1.5Mp, inlet temperature is 125-175 DEG C, and outlet temperature is 160-210 DEG C, and air speed is 0.75h-1, high-pressure separator operates
Pressure is 2.0Mp.
A kind of environmentally friendly solvent the most according to claim 1 and 2 and partial monosomy alkane process units and using method thereof,
It is characterized in that: two adsorptive reactors are set, during operation one open one standby, ZnO, MgO, CaO adsorption catalyst exchange in turn or
Using by proportioning, it is simple to not parking more catalyst changeout, rectifying column tower bottom reboiler thermal source uses 1.2Mpa, 220 DEG C of conduction oils, its
In de-lighter hydrocarbons column overhead temperatures be 43.5-52 DEG C, column bottom temperature be 60-71 DEG C, operation pressure be 0.5Mpa, removing below C4 is gently
Component.
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| CN107964424A (en) * | 2017-12-05 | 2018-04-27 | 东营市俊源石油技术开发有限公司 | A kind of apparatus and method for being hydrogenated with rectifying separation joint-product customization feed naphtha |
| CN108238838A (en) * | 2016-12-26 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of method of C6 alkane high yield benzene |
| CN110105921A (en) * | 2019-04-28 | 2019-08-09 | 东营市俊源石油技术开发有限公司 | A kind of tasteless environment-friendly aerial fog propellant production equipment and production method |
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Application publication date: 20160921 |