CN102311790A - Liquid phase circular hydrogenation treatment method capable of improving mixed amount of hydrogen - Google Patents

Liquid phase circular hydrogenation treatment method capable of improving mixed amount of hydrogen Download PDF

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CN102311790A
CN102311790A CN2010102220760A CN201010222076A CN102311790A CN 102311790 A CN102311790 A CN 102311790A CN 2010102220760 A CN2010102220760 A CN 2010102220760A CN 201010222076 A CN201010222076 A CN 201010222076A CN 102311790 A CN102311790 A CN 102311790A
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storage equipment
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CN102311790B (en
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王喜彬
曾榕辉
孙万付
刘建宇
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a liquid phase circular hydrogenation treatment method capable of improving mixed amount of hydrogen. The process flow adopted by the method comprises that: a liquid-phase material ( including fresh raw material oil, after-reaction circulating oil and circulating oil in a supergravity hydrogen mixing equipment) and hydrogen are filled into the supergravity hydrogen mixing equipment at the same time; and the hydrogen is torn and cut into lots of micro air bubbles through the high-speed rotation of a gas-liquid mixing impeller, a gas-liquid mass transfer efficiency is increased greatly, hydrogen is dissolved in the liquid-phase material in a saturated state, and the lots of micro air bubbles are dispersed in the liquid-phase material in an emulsified state so as to be brought into a reactor to undergo a hydrogenation reaction. In the method disclosed by the invention, the adoption of the supergravity hydrogen mixing equipment greatly promotes the dissolution of hydrogen and more effectively removes gas-phase impurities such as hydrogen sulfide and ammonia, so as to promote reactions such as hydrodesulfurization, denitrification, aromatic saturation and cracking.

Description

A kind of method of liquid phase circulation hydrotreatment that mixes the hydrogen amount that improves
Technical field
The present invention relates to a kind of liquid phase round-robin hydroprocessing process, particularly improve the method for the liquid phase circulation hydrogenation of hydrogen meltage in the liquid phase material.
Background technology
Conventional fixed bed hydrogenation technology is the economical and effective means that remove impurity such as sulphur, nitrogen in the raw oil.In the operation of fixed bed hydrogenation device, often adopt higher hydrogen-oil ratio and hydrogen dividing potential drop, to guarantee the catalyst runs life-span, promote hydrogenating desulfurization, denitrogenation, aromatic hydrocarbons is saturated and the carrying out of reaction such as cracking.Yet the higher hydrogen gas circulating system of pressure needs high investment cost and running cost, has increased the oil manufacture cost indirectly.If can the hydrogen flowing quantity in the hydrotreatment process be reduced and save hydrogen gas circulating system and circulating hydrogen compressor, then can reduce the production cost of clean fuel for enterprise saves facility investment.
The perfect condition of fixed-bed reactor mass transfer is: raw oil is evenly distributed on the granules of catalyst surface, and hydrogen passes in the beds space.So hydrogen need be dissolved in the raw oil, could contact with catalyzer, participate in hydrogenation reaction.That is to say when higher hydrogen pressure of fixed bed hydrogenation process using and hydrogen-oil ratio operational condition; The wherein actual amounts of hydrogen that provides is considerably beyond the required amounts of hydrogen of chemical reaction; This operator scheme only is in order to strengthen the mass transfer power of hydrogen, to guarantee the hydrogen solubility in the raw oil.The mass transfer apparatus that present alternate transmission aspect is the most general mainly is tower class (comprising a reactor drum) equipment, and like tray column and packing tower etc., these operation of equipment are all accomplished under gravity field, and flowing of liquid phase mainly is the effect that receives gravity.Because gravity acceleration g is unalterable finite value, this has also just determined the basic act of liquid-flow from macroscopic view.On the one hand, liquid phase fluid flows with thicker stream layer in the mass transfer apparatus under the gravity field, and alternate transmission area renewal frequency is low and the transmission total area is less, makes alternate transmittance process be restricted; On the other hand, improve flow state and ability strengthening transfer process that gas speed can change liquid phase fluid, but receive the influence of liquid flooding, make that the raising of gas phase velocity is also very limited.
US6881326 has introduced a kind of two-phase hydrogenation preconditioning technique.Its technological process is that fresh feed oil, turning oil and hydrogen are dissolved in hydrogen in the oil through a mixed hydrogen production device, and the less reactor drum of oil entering of dissolving hydrogen contacts with catalyzer and carries out hydrogenation reaction, deviates from the impurity in the oil.A reaction back logistics part is circulated to mixed hydrogen production device, and a part is discharged from device as product.This method is dissolved in required hydrogen in the oil before adopting raw material and turning oil to get into reactor drum in advance, can omit the recycle hydrogen system.But should technology openly not dissolve the concrete mode of hydrogen, and after dissolving hydrogen, also be provided with the waste gas tripping device in the separator that before reactor drum, is provided with.Though can remove a small amount of waste gas that influences hydrogenation reaction (mainly being the hydrogen sulfide that removes after the reaction and ammonia etc.) like this; But the waste gas separating effect is relatively poor; Make partly that also dissolved hydrogen is separated from raw oil; Cause the solubleness of hydrogen in the raw oil to descend, finally influence hydrogenation and take off the impurity effect.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of liquid phase circulation method of hydrotreating that improves hydrogen meltage in the oil.Before raw oil gets into reactor drum; Be mixed into hypergravity gas-liquid mixed equipment with partial hydrogenation reaction back logistics earlier; Under the hypergravity condition; Hydrogen is dissolved in the liquid phase material with oversaturated state, and a large amount of microbubbles is scattered in the liquid phase material with emulsified state, is brought into reactor drum and carries out hydrogenation reaction.The present invention can simplify the operation course, and saves facility investment, and can improve the service efficiency of hydrogen, and good hydrogenation environment is provided.
The present invention improves the method for liquid phase circulation hydrotreatment that mixes the hydrogen amount and comprises following content:
A, employing vane type hypergravity mix hydrogen storage equipment; Hypergravity mixes the impeller high speed rotating in the hydrogen storage equipment; Form low pressure at the tubular shaft place; Liquid phase material (comprising the turning oil in fresh feed oil, reaction back turning oil and the mixed hydrogen storage equipment) and hydrogen are sucked, and under the effect of the inner hypergravity centrifuge field of impeller, hydrogen is torn by the high velocity liquid phase materials and is divided into great amount of bubbles.Wherein bigger bubble meeting fast rise coalescence is mixed the housing top of hydrogen storage equipment and discharges, through deviating from H by hypergravity 2S, NH 3Deng recycling behind the gaseous impurities.The liquid phase material that has fully dissolved hydrogen mixes the hydrogen storage equipment bottom from hypergravity and discharges;
The liquid phase material that b, step a discharge gets into hydrogenator and contacts the formation solid, liquid two-phase with catalyzer, carries out hydrogenation reaction;
C, a reacted logistics part are as the product discharger, and another part is circulated to hypergravity and mixes hydrogen storage equipment.
It is that gas, liquid two are operated mutually that the said hypergravity gas-liquid of step (a) is dissolved hydrogen storage equipment.The vane type hypergravity mixes the structure that hydrogen storage equipment employing impeller sense of rotation rear side is provided with qi-emitting hole, like the structure of patents such as CN200610134150.7, CN200610134149.4 introduction.Hydrogen gets into the mixed hydrogen storage equipment of hypergravity downwards by the top of tubular shaft, and liquid phase material upwards gets into the mixed hydrogen storage equipment of hypergravity by the bottom of tubular shaft.Because hydrogen is dissolved in the continuous circulation of liquid phase material that hypergravity mixes in the hydrogen storage equipment; Simultaneously through tubular shaft impeller high speed rotating; The a large amount of microbubbles that produce can increase the contact area of gas-liquid two-phase, and liquid phase material can form the saturated solution of hydrogen very soon, and the part ultramicro air bubble can be evenly distributed in the liquid phase material with emulsified state; Be brought into fixed-bed reactor, dissolving hydrogen further is provided.The service temperature that hypergravity mixes hydrogen storage equipment is controlled at 100~380 ℃, is preferably 150~330 ℃; Pressure 0.5~15.0MPa is preferably 2.5~10.0MPa; Vapour-liquid ratio (volume ratio under fresh feed and the inlet hydrogen standard state) is 1: 1~60: 1, is preferably 2.5: 1~15.0: 1.The volume ratio of circulation oil mass and fresh feed (recycle ratio) is 1: 1~10: 1, is preferably 2: 1~6: 1.
The said hydrogenator of step (b) is fixed-bed reactor.Its operational condition is: temperature of reaction is 200~420 ℃, volume space velocity 0.6~5.0h -1, be preferably 2.0~4.0h -1, reaction pressure is 0.5~15.0MPa, is preferably 2.5~10.0MPa.
The employed catalyzer of above-mentioned steps is that the conventional fixed bed hydrogenation in this area is handled catalyzer, wherein the activity of such catalysts metal can for nickel, cobalt, molybdenum or tungsten etc. one or more.Can comprise by weight percentage like the catalyzer composition: nickel or cobalt are 0.5%~10% (calculating by its oxide compound), and molybdenum or tungsten are 1%~30% (calculating by its oxide compound), and carrier can be aluminum oxide; Silicon oxide; Aluminium oxide-silicon oxide, titanium oxide waits one or more.Catalyzer is extrudate or sphere.The bulk density of catalyzer is 0.5~1.1g/cm 3, granules of catalyst diameter (spherical diameter or bar shaped diameter) is 0.04~1.0mm, specific surface area is 80~400m 2/ g.
The raw material that the present invention handles is the hydrocarbon raw material of boiling range any cut in 130~550 ℃ of scopes.Generally include one or more mixing of spray vapour fuel fraction, diesel oil distillate, catalytic cracking light cycle oil (LCO), wax tailings (CGO), light vacuum gas oil (LVGO), heavy vacuum gas oil (HVGO) etc.
Advantage of the present invention is:
1, under the condition of hypergravity; The a large amount of microbubbles that produce can increase the contact area of gas-liquid two-phase; Liquid phase material can form the saturated solution of hydrogen very soon, and the part ultramicro air bubble can be evenly distributed in the liquid phase material with emulsified state, is brought into fixed bed hydrogenation reactor.
2, in hypergravity mixes hydrogen storage equipment, when liquid phase material fully dissolves hydrogen, the H in can the effective elimination reaction system 2S, NH 3Deng gaseous impurities, promote reactions such as hydrogenating desulfurization, denitrogenation, aromatic hydrocarbons be saturated.
3, hydrogenating desulfurization, denitrogenation, aromatic hydrocarbons are saturated etc., and reaction all is thermopositive reaction, and bigger circulation oil mass can be taken a large amount of reaction heat out of, prevents that the reactor drum temperature rise is excessive.Carry enough hydrogen simultaneously and get into reactor drum, guarantee the quantity of the required hydrogen of reaction.
4, do not need the recycle hydrogen system.Just when dissolving hydrogen, use a spot of new hydrogen, hypergravity mixes the hydrogen storage equipment effluent air and removes H through separating 2S, NH 3Use Deng can continuing behind the gaseous impurities.
5, with respect to the transmission equipment such as tower under the gravity field, hypergravity mixes hydrogen storage equipment and has that volume is little, cost is low, the efficient advantages of higher.
Description of drawings
Fig. 1 is a process method schematic flow sheet of the present invention.
Among the figure: 1-fresh feed oil, the 2-fresh hydrogen, 3-contains H 2S, NH 3Deng the hydrogen of gaseous impurities, the 4-hypergravity mixes hydrogen storage equipment, the 5-gas-liquid mixing impeller, and 6-tubular shaft, 7-fully dissolve the liquid phase material of hydrogen, and 8-fixed bed hydrogenation reactor, 9-generate oil, 10-turning oil.
Embodiment
For further setting forth concrete characteristic of the present invention, will combine accompanying drawing explanation.
In conjunction with accompanying drawing 1, a kind of technological process of the present invention is:
Fresh feed oil 1, the turning oil that mixes in the hydrogen storage equipment from the turning oil 10 and the hypergravity of hydrogenator are inhaled into gas-liquid mixing impeller 5 in the bottom of tubular shaft 6; Mix the back with fresh hydrogen 2 and thrown away, under the condition of hypergravity, carry out liquid phase material and dissolve hydrogen and deviate from H by the impeller of high speed rotating 2S, NH 3Deng gaseous impurities.Wherein the service temperature of the mixed hydrogen storage equipment of hypergravity is controlled at 100~380 ℃, is preferably 150~330 ℃; Pressure 0.5~15.0MPa is preferably 2.5~10.0MPa; Vapour-liquid ratio (volume) is 1: 1~60: 1, is preferably 2.5: 1~15.0: 1.The volume ratio of circulation oil mass and fresh feed (recycle ratio) is 1: 1~10: 1, is preferably 2: 1~6: 1.Fully the liquid phase material 7 entering fixed-bed reactor 8 of dissolving hydrogen carry out catalytic hydrogenation reaction, and wherein the operational condition of fixed-bed reactor is: temperature of reaction is 260~420 ℃, volume space velocity 0.6~5.0h -1, be preferably 2.0~4.0h -1, reaction pressure is 0.5~15.0MPa, is preferably 2.5~10.0MPa.Reacted part generates oil 9 and discharges as product from device, and part logistics 10 loops back the hypergravity gas-liquid and dissolves hydrogen storage equipment 4.
For further specifying scheme of the present invention and effect, enumerate following examples and comparative example:
Embodiment 1-2
Present embodiment is a kind of embodiment that hydrocarbon oil hydrogenation is handled, and the operating process synoptic diagram is with reference to accompanying drawing 1.
Fresh feed oil 1, the turning oil that mixes in the hydrogen storage equipment from the turning oil 10 and the hypergravity of hydrogenator are inhaled into gas-liquid mixing impeller 5 in the bottom of tubular shaft 6; Mix the back with fresh hydrogen 2 and thrown away, under the condition of hypergravity, carry out liquid phase material and dissolve hydrogen and deviate from H by the impeller of high speed rotating 2S, NH 3Deng gaseous impurities.Through the H that contains that forms behind the mixed hydrogen storage equipment of hypergravity 2S, NH 3Hydrogen 3 Deng gaseous impurities is discharged from the housing top that hypergravity mixes hydrogen storage equipment, after purifying, recycles.Fully the liquid phase material 7 entering fixed-bed reactor 8 of dissolving hydrogen carry out catalytic hydrogenation reaction, and reacted part generates oil 9 and discharges as product from device, and part logistics 10 loops back the molten hydrogen storage equipment 4 of hypergravity gas-liquid.
Adopt feedstock property to see table 1-1, catalyzer is selected the FH-UDS Hydrobon catalyst of Fushun Petrochemical Research Institute's development and production for use.The composition of FH-UDS catalyzer and quality index are seen table 1-2, and processing condition are seen table 1-3, and refined diesel oil character is seen table 1-4.Dissolving the hydrogen gas-liquid volume ratio is 5: 1.
Table 1-1 raw oil character
Figure BSA00000180495800061
The composition and the quality index of table 1-2 catalyzer
Figure BSA00000180495800062
Table 1-3 processing condition
Processing condition Condition 1 Condition 2
Temperature of reaction, ℃ 360 360
Reaction pressure, MPa 5.5 5.5
Circulation volume ratio (turning oil: fresh feed) 3∶1 5∶1
Volume space velocity, h -1 3.0 3.0
Mix hydrogen amount/inlet amount (wt%) 0.72 0.72
Table 1-4 treated oil character
Figure BSA00000180495800071
Comparative example
Compare with embodiment, adopt common fillers tower (gas-liquid counter current operation) as dissolving hydrogen storage equipment, processing condition are seen table 2-1, and refined diesel oil character is seen table 2-2.
Table 2-1 processing condition
Figure BSA00000180495800072
Table 2-2 treated oil character
Figure BSA00000180495800081
Above result can find out; Adopt the contact area between hydrogen of the present invention and liquid phase material to increase, cause alternate transmittance process greatly to be strengthened, hydrogen can fully be dissolved in the liquid phase material with oversaturated state; Gaseous impurities removal efficiencies such as hydrogen sulfide and ammonia improve greatly simultaneously; Make the hydrogenation reaction performance obviously improve, improve 30 percentage points, obtained beyond thought technique effect like desulfurization degree.

Claims (6)

1. one kind is improved the method for liquid phase circulation hydrotreatment that mixes the hydrogen amount, it is characterized in that comprising following content:
A, employing vane type hypergravity mix hydrogen storage equipment; Hypergravity mixes the impeller high speed rotating in the hydrogen storage equipment, forms low pressure at the tubular shaft place, and liquid phase material and hydrogen are sucked; Under the effect of the inner hypergravity centrifuge field of impeller, hydrogen is torn by the high velocity liquid phase materials and is divided into great amount of bubbles;
The liquid phase material that b, step a discharge gets into hydrogenator and contacts the formation solid, liquid two-phase with catalyzer, carries out hydrogenation reaction;
C, a reacted logistics part are as the product discharger, and another part is circulated to hypergravity and mixes hydrogen storage equipment.
2. according to the described method of claim 1, it is characterized in that: the liquid phase material described in the step a comprises fresh feed oil and reaction back turning oil.
3. according to the described method of claim 1, it is characterized in that: it is that gas, liquid two are operated mutually that the said hypergravity gas-liquid of step a is dissolved hydrogen storage equipment, and the vane type hypergravity mixes hydrogen storage equipment and adopts impeller sense of rotation rear side that the structure of qi-emitting hole is set.
4. according to the described method of claim 1; It is characterized in that: the service temperature that hypergravity mixes hydrogen storage equipment is controlled at 100~380 ℃; Pressure 0.5~15.0MPa; Volume ratio under fresh feed and the inlet hydrogen standard state is 1: 1~60: 1, and the volume ratio of circulation oil mass and fresh feed is 1: 1~10: 1.
5. according to the described method of claim 1; It is characterized in that: the service temperature that hypergravity mixes hydrogen storage equipment is controlled to be 150~330 ℃; Pressure is 2.5~10.0MPa; Volume ratio under fresh feed and the inlet hydrogen standard state is 2.5: 1~15.0: 1, and the volume ratio of circulation oil mass and fresh feed is 2: 1~6: 1.
6. according to the described method of claim 1, it is characterized in that: the said hydrogenator of step b is fixed-bed reactor, and its operational condition is: temperature of reaction is 200~420 ℃, volume space velocity 0.6~5.0h -1, reaction pressure is 0.5~15.0MPa.
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