CN103787811A - Method for hydrotreating butadiene tail gas - Google Patents
Method for hydrotreating butadiene tail gas Download PDFInfo
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Abstract
The invention provides a method for hydrotreating alkynes-rich butadiene tail gas. The method comprises the following steps: butadiene tail gas is extracted, the tail gas is absorbed, a liquid phase of a Ni-based catalyst which takes a titania-alumina compound is performed with a hydrotreating reaction is employed, the gas phase hydrogenation reaction of a Ni-Mo catalyst is used, and steps of desorption and rectification are carried out. According to the invention, the hidden trouble when the liquefaction method of pressure rising and condensation are employed on the butadiene tail gas is eliminated by the method provided by the invention, alkene content in the hydrotreating products is obviously reduced, the alkene content is less than 5%, and the requirement for cracking the raw material can be reached.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to the method for hydrotreating that is rich in alkynes tail gas that a kind of butadiene extraction unit produces.
Background technology
1,3-butadiene in cracking c_4 cut is generally refined by the method for two sections of solvent extraction rectifying and conventional distillation, and this device produces the divinyl tail gas that is rich in alkynes.In divinyl tail gas, alkynes concentration is higher, is generally greater than 20 % by weight, the highest 40 % by weight that exceed.These waste gas that are rich in alkynes there is no at present industrial utilization and are worth, and can only send torch burning processing.Due to the easy polymerization blast of high density alkynes, after diluting, the raffinate that therefore general employing contains butane, butylene send torch burning, so just cause the very large wasting of resources.Along with the increasing of hydrocarbon vapours cracking severity in recent years, in cracking c_4, alkynes content is in rising trend, and the tail gas amount that is rich in alkynes that butadiene extraction unit produces also increases considerably.If the tail gas processing and utilization that these are rich in to alkynes, will improve the utilization ratio of hydrocarbon resources and the economic benefit of ethylene cracker greatly.
In prior art, divinyl tail gas adopts method of hydrotreating processing and utilization conventionally, and the rich alkynes salvage stores that can produce Butadiene Extraction utilizes.
Method is that the divinyl tail gas to being rich in alkynes is selected a hydrogenation, alkynes is converted into divinyl and monoolefine, then sends butadiene extraction unit back to, to reclaim divinyl wherein.CN200810239462.3 discloses the selection method of hydrotreating of the height unsaturated hydrocarbons in a kind of C-4-fraction, take the salvage stores that is rich in alkynes that obtains after Butadiene Extraction as raw material, under the existence of catalyzer, adopt fixed-bed reactor, select hydrogenation to obtain 1,3-divinyl, then reaction product is sent back to extraction plant.The operational condition that hydrogenation technique adopts is: temperature of reaction is 30 ~ 90 ℃, and reaction pressure is 1.0 ~ 4.0MPa, and liquid air speed is 7 ~ 20h
-1.The palladium series catalyst of catalyzer take aluminum oxide as carrier, specific surface area is 50 ~ 150m
2/ g, specific pore volume is 0.25 ~ 1.0ml/g.
Method be the hydrocarbon mixture that is rich in alkynes that produces take butadiene extraction unit as a raw material, make hydrogen and alkynes even divinyl react to remove even divinyl of alkynes, product can be used as fuel, also can further reclaim 1-butylene and other monoolefine.CN03159237.6 discloses the method for utilizing of the hydrocarbon mixture that is rich in alkynes that a kind of butadiene extraction unit produces, and hydrogen and alkynes even divinyl react to remove even divinyl of alkynes.The first stage reactor of the method is heat-insulating bubbling bed reactor, and catalyzer is two-pack or the multicomponent catalyst that contains group VIII metal; Second stage reactor is heat-insulating bubbling bed reactor, and catalyzer is to contain the catalyzer of group VIII metal as active ingredient.
The defect of above-mentioned prior art is:
(1) there is the problem of the liquefaction of divinyl tail gas and reactor feed in the method.Hydrogenation reaction is liquid phase reaction, and pressure is between 1.5 ~ 4.0MPa, and divinyl tail gas is gas phase, and pressure approaches normal pressure; Liquefying, boosting in process, because the concentration of alkynes in material and divinyl is high, easily polymerization is blasted, and how under the premise that security is guaranteed material to be liquefied, to be boosted is a technical barrier;
(2) catalyzer that the method adopts is two-pack or the multicomponent catalyst that contains group VIII metal, and when liquid-phase reaction condition, the transformation efficiency that C 4 olefin is converted into alkane is not high, and in product, olefin(e) centent is high, can not serve as cracking stock; And the life cycle of catalyzer is short, need to regenerate once every half a year, working cost is higher.
Summary of the invention
There is potential safety hazard for solving in the difficult liquefaction of the divinyl tail gas raw material existing in prior art, the liquefaction process that boosts, high with olefin(e) centent in product, the reactor operational cycle is short, catalyzer needs the problems such as frequent regeneration, the invention provides a kind of divinyl tail gas hydrogenation method.
The present invention adopts tail gas absorber, the hydrogenation reaction using titanium dioxide-aluminum oxide mixture as carrier with take nickel as active constituent catalyst, the combination of desorption tower, solve divinyl tail gas and adopted the potential safety hazard of boosting, existing when the liquifying method of condensation, the problem such as higher with olefin(e) centent in product after hydrogenation, working cost is higher, olefin(e) centent is less than 5%, reaches the requirement as ethylene unit cracking stock.
Divinyl tail gas hydrogenation method of the present invention is achieved in that
A method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
(1) solvent absorbing tail gas: enter tail gas absorber from the divinyl tail gas of butadiene extraction unit and absorb; Described absorption tower is packing tower, and divinyl tail gas enters absorption tower from tower bottom, and absorption agent enters absorption tower from top of tower; The mass flux ratio of described absorption agent and described divinyl tail gas is 4:1 ~ 20:1; Described absorption agent is selected from: one or more in toluene, dimethylbenzene, C5 hydrocarbon, C6 hydrocarbon, C8 hydrocarbon, pyrolysis gasoline;
(2) one-stage hydrogenation reaction: the tower bottoms phase materials on described absorption tower is boosted, with mix from the liquid phase material of one-stage hydrogenation reactor outlet separating tank, enter the top of one-stage hydrogenation reactor, excessive hydrogen enters the top of described one-stage hydrogenation reactor, one-stage hydrogenation reaction product enters described one-stage hydrogenation reactor outlet separating tank;
The catalyzer that described one-stage hydrogenation reactor adopts is take titanium dioxide-aluminum oxide mixture as carrier, the active ingredient being carried on described carrier is metallic nickel, described metallic nickel accounts for 5 ~ 35% of described total catalyst weight, and titanium oxide accounts for 5 ~ 40% of described titanium dioxide-aluminum oxide complexes carrier weight;
The temperature in of described one-stage hydrogenation reactor is 30 ~ 70 ℃, and reaction pressure is 2.2 ~ 2.9MPa, and volume liquid air speed is 1 ~ 16h
-1, recycle feed volume ratio is 5 ~ 40; Described hydrogen with enter the alkynes of described one-stage hydrogenation reactor, the mol ratio of diolefin is 1.5 ~ 8; Described recycle feed volume ratio is the ratio that one section of reaction product is circulated to the liquid phase of first stage reactor entrance and the tower bottoms phase materials amount on described absorption tower.
(3) secondary hydrogenation reaction: after mixing, heat from gas-phase product, Partial Liquid Phase product and the recycle hydrogen from second-stage hydrogenation reactor outlet separating tank of described one-stage hydrogenation reactor outlet separating tank; Enter second-stage hydrogenation reactor top; Secondary hydrogenation reaction product enters described second-stage hydrogenation reactor outlet separating tank after being cooled to 30 ~ 50 ℃;
The catalyzer that described second-stage hydrogenation reactor adopts is using titanium dioxide-aluminum oxide mixture as carrier, the active ingredient being carried on described carrier is metallic nickel and molybdenum, described metallic nickel accounts for 5 ~ 30% of described total catalyst weight, described metal molybdenum accounts for 1 ~ 10% of described total catalyst weight, and titanium oxide accounts for 5 ~ 40% of titanium dioxide-aluminum oxide complexes carrier weight;
The temperature in of described second-stage hydrogenation reactor is 170 ~ 250 ℃, and reaction pressure is 2.0-2.9MPa, enters the hydrogen of described second-stage hydrogenation reactor and the mol ratio of alkene 1.5 ~ 10.0; Volume gas phase air speed is 200 ~ 600h
-1;
(4) Desorption separation: the liquid product from described second-stage hydrogenation reactor outlet separating tank enters desorption tower; Described desorption tower is packing tower or tray column, working pressure is 0.8 ~ 1.5MPa, the liquid product that described desorption tower top obtains is the normal butane product that olefin(e) centent is less than 5%, and tower kettle product is the absorption agent of carbon containing four not, is recycled to described tail gas absorber after overcooling.
In the specific implementation, described divinyl tail gas contains: butane 0 ~ 5 % by weight, butylene 0 ~ 15 % by weight, divinyl 20 ~ 60 % by weight, ethylacetylene and vinylacetylene 20 ~ 50 % by weight.
In the specific implementation, in step (1), described tail gas absorber adopts structured packing Y250; Described absorption agent is that toluene is or/and C5; The mass flux ratio of described absorption agent and described divinyl tail gas is 7:1 ~ 15:1, preferred 8:1 ~ 13:1; The working pressure of described tail gas absorber is pressure-fired, and described absorption agent temperature is 30 ~ 50 ℃, preferably 32 ~ 42 ℃.Vinylacetylene concentration in divinyl tail gas is absorbed dilution agent to 10% following (absorbing tower reactor material medium vinyl acetylene content), to improve the safety performance that with pump, material is boosted to reaction pressure timer.
In the specific implementation, in step (2), selective hydrogenation reaction can be selected hydrogenation catalyst well known in the prior art, for example disclosed selective acetylene hydrocarbon hydrogenation catalyst in CN201010544652.3, described catalyzer is preferably using titanium dioxide-aluminum oxide mixture as support of the catalyst, its active ingredient is nickel, and described nickel content accounts for described catalyst weight preferably 10 ~ 30%, preferably 10 ~ 25%.The preferred temperature in of described one-stage hydrogenation reactor is 40 ~ 60 ℃, and volume liquid air speed is 2 ~ 10h
-1, recycle feed volume ratio is 8 ~ 30; Described hydrogen with enter the alkynes of described one-stage hydrogenation reactor, the mol ratio of diolefin is 2 ~ 6.In first stage reactor, alkynes, the full hydrogenation of diolefine, generate corresponding alkene and alkane.Total alkynes, diolefin content in hydrogenation after product are less than 10ppm.In first stage reactor, alkynes, diolefine are all converted into alkene, and catalyzer life cycle is no less than 4 years.
In the specific implementation, in step (3), full hydrogenation reaction can be selected the selective hydrogenation catalyst in known technology, described catalyzer is preferably using titanium dioxide-aluminum oxide mixture as support of the catalyst, active ingredient is the two components of nickel and molybdenum, and described nickel and molybdenum account for described catalyst weight preferably 5 ~ 30 and 1 ~ 10%, more preferably 15 ~ 20% and 3 ~ 6%.The temperature in of described second-stage hydrogenation reactor is 180 ~ 230 ℃, and reaction pressure is 2.1 ~ 2.8MPa, described hydrogen and the mol ratio 2 ~ 8 that enters the alkene of described second-stage hydrogenation reactor; Volume gas phase air speed is 300 ~ 500h
-1.In second stage reactor, most of hydrogenation of olefins is converted into alkane.In second stage reactor, most of conversion of olefines is alkane, and catalyzer life cycle is no less than 4 years;
In the specific implementation, in step (4), working pressure is 1.0 ~ 1.4MPa.Described desorption tower top obtains the normal butane product that olefin(e) centent is less than 5%, to reduce the carbon four losing in the non-condensable gas of tail gas absorber top, tower reactor is the poor absorption agent containing a small amount of carbon four, and wherein carbon four content are less than 5%, and poor absorption agent is recycled to described tail gas absorber after overcooling.
The divinyl tail gas hydrogenation method providing of the present invention, first, under the pressure that approaches normal pressure, adopts desorb tower reactor material to absorb divinyl tail gas as absorption agent, and absorption agent can also be toluene, dimethylbenzene, C5, C6, C8 hydrocarbon, pyrolysis gasoline or its mixture; Then through one section of liquid-phase hydrogenatin, two sections of gas phase hydrogenations, excess hydrogen compression cycle is used; Then second-stage reaction product, in desorption tower rectifying, finally obtains from desorb tower top the normal butane that olefin(e) centent is less than 5%.
While adopting step (1) ~ (2) of the inventive method, alkynes, diolefine and hydrogen generation selective hydrogenation reaction in tail gas, generate monoolefine, and product can be sent to 1-butylene retrieving arrangement and reclaim monoolefine; In the time adopting step (1) ~ (4) of the inventive method, the alkynes in tail gas, diolefin, monoolefin hydrogenation generate alkane, and hydrogenation products can substitute petroleum naphtha as the cracking stock of ethylene unit.
The tail gas that is rich in alkynes that the present invention discharges take butadiene extraction unit is the cracking stock of raw materials for ethylene production device, replaces petroleum naphtha, has good economic benefit.After tail gas absorbs with absorption agent, absorption liquid medium vinyl concentration of acetylene reduces, then boost with pump, and device safe.The reaction of employing two-stage hydrogenation, one-stage hydrogenation reaction adopts Ni catalyst based, and secondary hydrogenation reaction adopts Ni-MO type catalyzer, and in product, olefin(e) centent is few, and Determination of Alkane Content is high, and catalyzer life cycle and life-span are long, without regeneration.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of divinyl tail gas hydrogenation method of the present invention.
Nomenclature:
1 divinyl tail gas; 2 tail gas absorbers; 3 unabsorbed tail gas; 4 absorb tower reactor material; 5 fresh feed pumps; 6 circulation fluids; 7 hydrogen; 8 one-stage hydrogenation reactors; 9 one-stage hydrogenation reactor products; 10 one section outlet separating tanks; 11 recycle pumps; 12 recirculation coolers; 13 one section outlet separating tanks go the liquid phase of two sections; 14 one section outlet separating tanks go the gas phase of two sections; 15 circulating hydrogens; 16 2 sections of entrance well heaters; 17 second-stage hydrogenation reactor chargings; 18 second-stage hydrogenation reactors; 19 second-stage hydrogenation reactor products; 20 second stage exit water coolers; 21 second stage exit separating tanks; 22 second stage exit separating tank liquid phases are removed desorption tower; The non-condensable gas of 23 discharges; 24 recycle hydrogens; 25 circulating hydrogen compressors; 26 desorption towers; 27 condensers; 28 return tanks; 29 reflux pumps; 30 high density normal butane products; 31 non-condensable gases; 32 desorb tower reactor materials; 33 absorption agent water coolers; 34 absorption agents; 35 reboilers
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with drawings and Examples, protection scope of the present invention is not limited to following embodiment.
Embodiment 1
From the divinyl tail gas 1 of butadiene extraction unit, pressure 5KPaG, 30 ℃ of temperature, flow 1000kg/h, enters from the bottom of tail gas absorber 2.The absorption agent 34 coming from desorb tower reactor enters from tail gas absorber 2 jackings, and absorption agent is toluene, and flow is 12030kg/h.Unabsorbed tail gas 3 is discharged from tower top, be absorbed the divinyl tail gas that gets off and the mixture 4 use fresh feed pumps 5 of absorption agent and boost to 2.9MPaG, mix with the recycle stock 6 of one section outlet separating tank 10, enter from the top of first stage reactor 8, the flow of recycle stock 6 is 25000kg/h, 40 ℃ of temperature.Hydrogen 7 pressure 3.0MPaG, flow 125kg/h, enters from first stage reactor 8 tops.The entry condition of first stage reactor is: 40 ℃ of temperature, pressure 2.85MPa, hydrogen in hydrogen/(alkynes+diolefine) mol ratio 2.5:1(hydrogen 7: alkynes+diolefine in divinyl tail gas 1), liquid phase volume air speed 5h
-1, one section of reaction product 9 enters one section outlet separating tank 10, a liquid phase part through recycle pump 11 boost, recirculation cooler 12 mixes with fresh feed pump 5 outlet materials after cooling.Another liquid phase material 13 mixes with gaseous phase materials 14, the recycle hydrogen 15 of tank top, is heated to 225 ℃ through two sections of entrance well heaters 16, enters from second stage reactor 18 tops.The entry condition of second stage reactor is: 225 ℃ of temperature, pressure 2.7MPa, hydrogen in bis-sections of entrances 17 of hydrogen/olefin molar ratio 4.9:1(: alkene), gaseous phase volume air speed 300h
-1.Outlet material 19 is water-cooled to 40 ℃ in second stage exit water cooler 20 use, enter into second stage exit separating tank 21, gas phase is divided into two strands, most of gas phase 24 is returned to second stage reactor entrance after compressor 25 compressions, small portion gas phase 23 is sent battery limit (BL), pot bottom liquid phase 22 enters into desorption tower 26 middle parts, tower top C-4-fraction enters into return tank 28 after condenser 27 is cooling, non-condensable gas 31 dischargers, a phlegma part is back to tower top after boosting with pump, the normal butane product 30 that a part is less than 5% for olefin(e) centent, flow is 989kg/h.Tower reactor material 32 is the toluene containing a small amount of carbon four, delivers to tail gas absorber top and recycle after supercooler 33 is cooling.
The quality group prejudice table 1 of each main streams.
Table 1
Continued 1
Divinyl tail gas medium vinyl acetylene content higher (concentration of logistics 1 medium vinyl acetylene is 40.51%), pressure lower (5KPaG).As adopted, gas blower boosts, the method for condensation liquefaction divinyl tail gas, then boosts to reaction pressure (2.2 ~ 2.9MPaG) with pump, and because vinylacetylene content is high, device exists potential safety hazard.The method liquefaction divinyl tail gas that this patent adopts normal pressure to absorb, divinyl tail gas absorber filling 250Y filler, the resistance of tower is little, and pressure drop is 2KPaG; Absorption agent is toluene, and absorption agent temperature is 38.5 ℃, and the mass flux ratio of absorption agent and divinyl tail gas is 12:1, and divinyl tail gas recycle rate reaches 98%; Absorb, the concentration low (approximately 5%) of divinyl tail gas (absorb tower reactor material 4) medium vinyl acetylene after liquefaction, now boost to reaction pressure (2.2 ~ 2.9MPaG) with pump very safe.
The catalyzer that one-stage hydrogenation reactor adopts is take titanium dioxide-aluminum oxide mixture as carrier, the active ingredient being carried on complexes carrier is metallic nickel, the content of metallic nickel account for catalyzer gross weight 18%, the content of titanium oxide account for titanium dioxide-aluminum oxide complexes carrier weight 30%.
The temperature in of one-stage hydrogenation reactor is 40 ℃, and reaction pressure is 2.85MPa, and volume liquid air speed is 5h
-1, recycle feed volume ratio is 25, hydrogen with enter the alkynes of described one-stage hydrogenation reactor, the mol ratio of diolefin is 2.5, reactor outlet alkynes, diene content are less than 10ppm.
The catalyzer that second-stage hydrogenation reactor adopts is using titanium dioxide-aluminum oxide mixture as carrier, active ingredient is metallic nickel and molybdenum, the content of metallic nickel account for catalyzer gross weight 18%, the content of metal molybdenum account for catalyzer gross weight 5%, the content of titanium oxide account for titanium dioxide-aluminum oxide complexes carrier weight 35%.
The temperature in of second-stage hydrogenation reactor is 225 ℃, and reaction pressure is 2.7MPa, hydrogen and the mol ratio 4.9 that enters the alkene of described second-stage hydrogenation reactor; Volume gas phase air speed is 300h
-1.
Secondary hydrogenation product enters desorption tower, this tower working pressure 1.24MPaG,, by desorb, the liquid product (logistics 30) obtaining from tower top, normal butane content is up to 92.14%, and olefin(e) centent is 3.65%, and this material is applicable to doing the cracking stock of ethylene unit; The poor absorption agent (logistics 32) obtaining from tower reactor, carbon four content are 3.83%, deliver to tail gas absorber top and recycle after overcooling.
Claims (9)
1. a method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
(1) solvent absorbing tail gas: enter tail gas absorber from the divinyl tail gas of butadiene extraction unit and absorb; Described absorption tower is packing tower, and divinyl tail gas enters absorption tower from tower bottom, and absorption agent enters absorption tower from top of tower; The mass flux ratio of described absorption agent and described divinyl tail gas is 4:1 ~ 20:1; Described absorption agent is selected from: one or more in toluene, dimethylbenzene, C5 hydrocarbon, C6 hydrocarbon, C8 hydrocarbon and pyrolysis gasoline;
(2) one-stage hydrogenation reaction: the tower bottoms phase materials on described absorption tower is boosted, with mix from the liquid phase material of one-stage hydrogenation reactor outlet separating tank, enter the top of one-stage hydrogenation reactor, excessive hydrogen enters the top of described one-stage hydrogenation reactor, and one-stage hydrogenation reaction product enters described one-stage hydrogenation reactor outlet separating tank;
The catalyzer that described one-stage hydrogenation reactor adopts is take titanium dioxide-aluminum oxide mixture as carrier, the active ingredient being carried on described carrier is metallic nickel, described metallic nickel accounts for 5 ~ 35% of described total catalyst weight, and titanium oxide accounts for 5 ~ 40% of described titanium dioxide-aluminum oxide complexes carrier weight;
The temperature in of described one-stage hydrogenation reactor is 30 ~ 70 ℃, and reaction pressure is 2.2 ~ 2.9MPa, and volume liquid air speed is 1 ~ 16h
-1, recycle feed volume ratio is 5 ~ 40; Described hydrogen with enter the alkynes of described one-stage hydrogenation reactor, the mol ratio of diolefin is 1.5 ~ 8; Described recycle feed volume ratio is the ratio that one section of reaction product is circulated to the liquid phase of first stage reactor entrance and the tower bottoms phase materials amount on described absorption tower;
(3) secondary hydrogenation reaction: after mixing, heat from gas-phase product, Partial Liquid Phase product and the recycle hydrogen from second-stage hydrogenation reactor outlet separating tank of described one-stage hydrogenation reactor outlet separating tank; Enter second-stage hydrogenation reactor top; Secondary hydrogenation reaction product enters described second-stage hydrogenation reactor outlet separating tank after being cooled to 30 ~ 50 ℃;
The catalyzer that described second-stage hydrogenation reactor adopts is using titanium dioxide-aluminum oxide mixture as carrier, the active ingredient being carried on described carrier is metallic nickel and molybdenum, described metallic nickel accounts for 5 ~ 30% of described total catalyst weight, described metal molybdenum accounts for 1 ~ 10% of described total catalyst weight, and titanium oxide accounts for 5 ~ 40% of titanium dioxide-aluminum oxide complexes carrier weight;
The temperature in of described second-stage hydrogenation reactor is 170 ~ 250 ℃, and reaction pressure is 2.0-2.9MPa, enters the hydrogen of described second-stage hydrogenation reactor and the mol ratio of alkene 1.5 ~ 10.0; Volume gas phase air speed is 200 ~ 600h
-1;
(4) Desorption separation: the liquid product from described second-stage hydrogenation reactor outlet separating tank enters desorption tower; Described desorption tower is packing tower or tray column, working pressure is 0.8 ~ 1.5MPa, the liquid product that described desorption tower top obtains is the normal butane product that olefin(e) centent is less than 5%, and tower kettle product is the absorption agent of carbon containing four not, is recycled to described tail gas absorber after overcooling.
2. method of hydrotreating according to claim 1, is characterized in that:
Described divinyl tail gas contains: butane 0 ~ 5 % by weight, butylene 0 ~ 15 % by weight, divinyl 20 ~ 60 % by weight, ethylacetylene and vinylacetylene 20 ~ 50 % by weight.
3. method of hydrotreating according to claim 1, is characterized in that:
In step (1), described tail gas absorber adopts structured packing Y250; Described absorption agent is that toluene is or/and C5; The mass flux ratio of described absorption agent and described divinyl tail gas is 7:1 ~ 15:1; The working pressure of described tail gas absorber is pressure-fired, and described absorption agent temperature is 30 ~ 50 ℃.
4. method of hydrotreating according to claim 3, is characterized in that:
The mass flux ratio of described absorption agent and described divinyl tail gas is 8:1 ~ 13:1; Described absorption agent temperature is 32 ~ 42 ℃.
5. method of hydrotreating according to claim 1, is characterized in that:
In step (2), described metallic nickel accounts for 10 ~ 30% of described total catalyst weight; The temperature in of described one-stage hydrogenation reactor is 40 ~ 60 ℃, and volume liquid air speed is 2 ~ 10h
-1, recycle feed volume ratio is 8 ~ 30; Described hydrogen with enter the alkynes of described one-stage hydrogenation reactor, the mol ratio of diolefin is 2 ~ 6.
6. method of hydrotreating according to claim 5, is characterized in that:
Described metallic nickel accounts for 10 ~ 25% of described total catalyst weight.
7. method of hydrotreating according to claim 1, is characterized in that:
In step (3), described metallic nickel and described metal molybdenum account for respectively 8 ~ 25% and 2 ~ 8% of described total catalyst weight; The temperature in of described second-stage hydrogenation reactor is 180 ~ 230 ℃, and reaction pressure is 2.1 ~ 2.8MPa, described hydrogen and the mol ratio 2 ~ 8 that enters the alkene of described second-stage hydrogenation reactor; Volume gas phase air speed is 300 ~ 500h
-1.
8. method of hydrotreating according to claim 7, is characterized in that:
Described metallic nickel and described metal molybdenum account for respectively 15 ~ 20% and 3 ~ 6% of described total catalyst weight.
9. method of hydrotreating according to claim 1, is characterized in that:
In step (4), working pressure is 1.0 ~ 1.4MPa.
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