CN103787811B - A kind of method of hydrotreating of divinyl tail gas - Google Patents
A kind of method of hydrotreating of divinyl tail gas Download PDFInfo
- Publication number
- CN103787811B CN103787811B CN201210424643.XA CN201210424643A CN103787811B CN 103787811 B CN103787811 B CN 103787811B CN 201210424643 A CN201210424643 A CN 201210424643A CN 103787811 B CN103787811 B CN 103787811B
- Authority
- CN
- China
- Prior art keywords
- tail gas
- stage hydrogenation
- hydrogenation reactor
- tower
- divinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides the method for hydrotreating that a kind of butadiene extraction unit is rich in alkynes tail gas.Butadiene Extraction tail gas, first carries out tail gas absorption, the liquid-phase hydrogenatin reaction then adopting the Ni using Titanium oxide-aluminum oxide compound as carrier catalyst based, and the gas phase hydrogenation reaction adopting Ni-MO type catalyst based, then carries out desorb rectifying.The method not only eliminate divinyl tail gas adopt boosting, condensation liquifying method time the potential safety hazard that exists, and significantly reduce olefin(e) centent in hydrogenation products, olefin(e) centent is less than 5%, reaches the requirement as ethylene unit cracking stock.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to the method for hydrotreating being 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 being rich in alkynes.In divinyl tail gas, alkyne concentration is higher, is generally greater than 20 % by weight, the highest more than 40 % by weight.These waste gas being rich in alkynes there is no industrial utility value at present, can only send torch burning process.Because high density alkynes is easily polymerized blast, therefore the raffinate of general employing containing butane, butylene send torch burning after diluting, and so just causes 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 being rich in alkynes that butadiene extraction unit produces also increases considerably.If these to be rich in the tail gas processing and utilization of alkynes, the utilization ratio of hydrocarbon resources and the economic benefit of ethylene cracker greatly will be improved.
In prior art, divinyl tail gas adopts method of hydrotreating processing and utilization usually, can utilize the rich alkynes salvage stores that Butadiene Extraction produces.
Method carries out a selec-tive hydrogenation to the divinyl tail gas being rich in alkynes, alkynes is converted into divinyl and monoolefine, then sends butadiene extraction unit back to, to reclaim divinyl wherein.CN200810239462.3 discloses the selec-tive hydrogenation method of the height unsaturated hydrocarbons in a kind of C-4-fraction, with the salvage stores being rich in alkynes obtained after Butadiene Extraction for raw material, in the presence of a catalyst, adopt fixed-bed reactor, selec-tive hydrogenation obtains 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 DEG C, and reaction pressure is 1.0 ~ 4.0MPa, and liquid air speed is 7 ~ 20h
-1.Catalyzer take aluminum oxide as the palladium series catalyst of carrier, and specific surface area is 50 ~ 150m
2/ g, specific pore volume is 0.25 ~ 1.0ml/g.
Method be the hydrocarbon mixture being rich in alkynes that produces with butadiene extraction unit for a raw material, make hydrogen and alkynes even divinyl react to remove alkynes even divinyl, product can be used as fuel, also can reclaim 1-butylene and other monoolefine further.CN03159237.6 discloses the Application way being rich in the hydrocarbon mixture of alkynes that a kind of butadiene extraction unit produces, and hydrogen and alkynes even divinyl react to remove alkynes even divinyl.The first stage reactor of the method is heat-insulating bubbling bed reactor, and catalyzer is two-pack containing group VIII metal or multicomponent catalyst; Second stage reactor is heat-insulating bubbling bed reactor, and catalyzer is containing 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 is close to normal pressure; In liquefaction, boost process, because the concentration of alkynes in material and divinyl is high, easily polymerization is blasted, and how being liquefied by material under the premise that security is guaranteed, boosting is a technical barrier;
(2) catalyzer that the method adopts is two-pack containing group VIII metal or multicomponent catalyst, and during 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 as cracking stock; And the life cycle of catalyzer is short, every half a year need regeneration once, working cost is higher.
Summary of the invention
Potential safety hazard is there is for solving in the divinyl tail gas raw material difficulty liquefaction existed 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, be the hydrogenation reaction of active constituent catalyst, the combination of desorption tower using Titanium oxide-aluminum oxide compound as carrier with nickel, solve divinyl tail gas adopt boosting, condensation liquifying method time the potential safety hazard that exists, 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: the divinyl tail gas from butadiene extraction unit enters tail gas absorber and absorbs; 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, mix with the liquid phase material from 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 take Titanium oxide-aluminum oxide compound as carrier, the active ingredient be 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 oxide-aluminum oxide compound vehicle weight;
The temperature in of described one-stage hydrogenation reactor is 30 ~ 70 DEG C, 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 phases doses on described absorption tower.
(3) secondary hydrogenation reaction: from the gas-phase product of described one-stage hydrogenation reactor outlet separating tank, Partial Liquid Phase product and from after the recycle hydrogen mixing of second-stage hydrogenation reactor outlet separating tank, heating; 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 DEG C;
The catalyzer that described second-stage hydrogenation reactor adopts is using Titanium oxide-aluminum oxide compound as carrier, the active ingredient be 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 oxide-aluminum oxide compound vehicle weight;
The temperature in of described second-stage hydrogenation reactor is 170 ~ 250 DEG C, and reaction pressure is 2.0-2.9MPa, enters the hydrogen of described second-stage hydrogenation reactor and the mol ratio 1.5 ~ 10.0 of alkene; 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 not carbon containing four, through overcooling Posterior circle to described tail gas absorber.
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, preferably 8:1 ~ 13:1; The working pressure of described tail gas absorber is pressure-fired, and described absorption agent temperature is 30 ~ 50 DEG C, preferably 32 ~ 42 DEG C.Vinylacetylene concentration in divinyl tail gas is diluted to less than 10% (namely absorbing kettle material medium vinyl acetylene content), to improve the safety performance with pump, material being boosted to reaction pressure timer by absorption agent.
In the specific implementation, in step (2), selective hydrogenation reaction can select hydrogenation catalyst well known in the prior art, such as selective acetylene hydrocarbon hydrogenation catalyst disclosed in CN201010544652.3, described catalyzer is preferably using Titanium oxide-aluminum oxide compound 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 DEG C, 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 in hydrogenation after product, diolefin content 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 select the selective hydrogenation catalyst in known technology, described catalyzer is preferably using Titanium oxide-aluminum oxide compound as support of the catalyst, active ingredient is the two component 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 DEG C, and reaction pressure is 2.1 ~ 2.8MPa, described hydrogen and the mol ratio 2 ~ 8 of alkene entering 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 lost in tail gas absorption tower top non-condensable gas, tower reactor is the poor absorption agent containing a small amount of carbon four, and wherein carbon four content is less than 5%, poor absorption agent through overcooling Posterior circle to described tail gas absorber.
The divinyl tail gas hydrogenation method provided of the present invention, first close under the pressure of normal pressure, adopt desorb kettle material to absorb divinyl tail gas as absorption agent, 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 uses; Then second-stage reaction product is in desorption tower rectifying, finally obtains from desorb tower top the normal butane that olefin(e) centent is less than 5%.
When adopting step (1) ~ (2) of the inventive method, the alkynes in tail gas, diolefine and hydrogen generation selective hydrogenation reaction, generate monoolefine, and product can be sent to 1-butylene retrieving arrangement and reclaim monoolefine; When adopting step (1) ~ (4) of the inventive method, the alkynes in tail gas, diolefin, monoolefin hydrogenation generate alkane, and the cracking stock that hydrogenation products can be used as ethylene unit carrys out alternative petroleum naphtha.
The cracking stock that the tail gas being rich in alkynes that the present invention discharges with butadiene extraction unit is 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, and then with pump boosting, the security of device is high.Employing two-stage hydrogenation reacts, and 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, catalyzer life cycle and the life-span long, without the need to regenerating.
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 kettle 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 inlet heater; 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 remove 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 kettle material; 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, temperature 30 DEG C, flow 1000kg/h, enters from the bottom of tail gas absorber 2.The absorption agent 34 come from desorb tower reactor enters from tail gas absorber 2 jacking, and absorption agent is toluene, and flow is 12030kg/h.Unabsorbed tail gas 3 is discharged from tower top, 2.9MPaG is boosted to by mixture 4 fresh feed pump 5 of the divinyl tail gas that absorbs and absorption agent, 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, temperature 40 DEG C.Hydrogen 7 pressure 3.0MPaG, flow 125kg/h, enter from first stage reactor 8 top.The entry condition of first stage reactor is: temperature 40 DEG C, 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, and a liquid phase part is boosted through recycle pump 11, recirculation cooler 12 mixes with fresh feed pump 5 outlet material after cooling.Gaseous phase materials 14, the recycle hydrogen 15 of another liquid phase material 13 and tank top mix, and be heated to 225 DEG C, enter from second stage reactor 18 top through two sections of inlet heater 16.The entry condition of second stage reactor is: temperature 225 DEG C, pressure 2.7MPa, hydrogen in hydrogen/olefin molar ratio 4.9:1(bis-sections of entrances 17: alkene), gaseous phase volume air speed 300h
-1.Outlet material 19 at second stage exit water cooler 20 with being water-cooled to 40 DEG C, enter into second stage exit separating tank 21, gas phase is divided into two strands, major part gas phase 24 returns second stage reactor entrance after compressor 25 compresses, small portion gas phase 23 sends battery limit (BL), pot bottom liquid phase 22 enters in the middle part of desorption tower 26, tower top C-4-fraction enters into return tank 28 after condenser 27 cools, non-condensable gas 31 discharger, tower top is back to after the boosting of phlegma part pump, the normal butane product 30 that a part is less than 5% for olefin(e) centent, flow is 989kg/h.Kettle material 32 is the toluene containing a small amount of carbon four, delivers to tail gas absorption tower top and recycle after supercooler 33 cools.
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, and then boost to reaction pressure (2.2 ~ 2.9MPaG) with pump, because vinylacetylene content is high, device exists potential safety hazard.This patent adopts the method liquefaction divinyl tail gas of ordinary-pressure absorption, divinyl tail gas absorber filling 250Y filler, and the resistance of tower is little, and pressure drop is 2KPaG; Absorption agent is toluene, and absorption agent temperature is 38.5 DEG C, 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 (about 5%) of the divinyl tail gas of post liquefaction (absorbing kettle material 4) medium vinyl acetylene, now boost to reaction pressure (2.2 ~ 2.9MPaG) with pump very safe.
The catalyzer that one-stage hydrogenation reactor adopts take Titanium oxide-aluminum oxide compound as carrier, the active ingredient be carried on complexes carrier is metallic nickel, the content of metallic nickel accounts for 18% of the gross weight of catalyzer, and the content of titanium oxide accounts for 30% of the weight of Titanium oxide-aluminum oxide compound carrier.
The temperature in of one-stage hydrogenation reactor is 40 DEG C, 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 oxide-aluminum oxide compound as carrier, active ingredient is metallic nickel and molybdenum, the content of metallic nickel accounts for 18% of the gross weight of catalyzer, the content of metal molybdenum accounts for 5% of the gross weight of catalyzer, and the content of titanium oxide accounts for 35% of the weight of Titanium oxide-aluminum oxide compound carrier.
The temperature in of second-stage hydrogenation reactor is 225 DEG C, and reaction pressure is 2.7MPa, hydrogen and the mol ratio 4.9 of alkene entering 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, from the liquid product (logistics 30) that tower top obtains, normal butane content is up to 92.14%, and olefin(e) centent is 3.65%, and this material is applicable to the cracking stock making ethylene unit; From the poor absorption agent (logistics 32) that tower reactor obtains, carbon four content is 3.83%, delivers to tail gas absorption tower top and recycle after overcooling.
Claims (9)
1. a method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
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;
(1) solvent absorbing tail gas: the divinyl tail gas from butadiene extraction unit enters tail gas absorber and absorbs; 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, 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, mix with the liquid phase material from 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 take Titanium oxide-aluminum oxide compound as carrier, the active ingredient be 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 oxide-aluminum oxide compound vehicle weight;
The temperature in of described one-stage hydrogenation reactor is 30 ~ 70 DEG C, 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 phases doses on described absorption tower;
(3) secondary hydrogenation reaction: from the gas-phase product of described one-stage hydrogenation reactor outlet separating tank, Partial Liquid Phase product and from after the recycle hydrogen mixing of second-stage hydrogenation reactor outlet separating tank, heating; 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 DEG C;
The catalyzer that described second-stage hydrogenation reactor adopts is using Titanium oxide-aluminum oxide compound as carrier, the active ingredient be 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 oxide-aluminum oxide compound vehicle weight;
The temperature in of described second-stage hydrogenation reactor is 170 ~ 250 DEG C, and reaction pressure is 2.0-2.9MPa, enters the hydrogen of described second-stage hydrogenation reactor and the mol ratio 1.5 ~ 10.0 of alkene; 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 not carbon containing four, through overcooling Posterior circle to described tail gas absorber.
2. method of hydrotreating according to claim 1, is characterized in that: described absorption agent is dimethylbenzene.
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 DEG C.
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 DEG C.
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 DEG C, 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 8 ~ 25% and 2 ~ 8% of described total catalyst weight respectively; The temperature in of described second-stage hydrogenation reactor is 180 ~ 230 DEG C, and reaction pressure is 2.1 ~ 2.8MPa, described hydrogen and the mol ratio 2 ~ 8 of alkene entering 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 15 ~ 20% and 3 ~ 6% of described total catalyst weight respectively.
9. method of hydrotreating according to claim 1, is characterized in that:
In step (4), working pressure is 1.0 ~ 1.4MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210424643.XA CN103787811B (en) | 2012-10-30 | 2012-10-30 | A kind of method of hydrotreating of divinyl tail gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210424643.XA CN103787811B (en) | 2012-10-30 | 2012-10-30 | A kind of method of hydrotreating of divinyl tail gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103787811A CN103787811A (en) | 2014-05-14 |
| CN103787811B true CN103787811B (en) | 2015-09-16 |
Family
ID=50663930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210424643.XA Active CN103787811B (en) | 2012-10-30 | 2012-10-30 | A kind of method of hydrotreating of divinyl tail gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103787811B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307301B (en) * | 2014-07-24 | 2016-03-30 | 襄阳航力机电技术发展有限公司 | A kind of butadiene device for recovering tail gas and recovery method thereof |
| US9566548B2 (en) | 2015-06-24 | 2017-02-14 | International Business Machines Corporation | Butadiene sequestration via sulfur dioxide charged zeolite beds |
| CN106467451B (en) * | 2015-08-19 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of method of coproduction isobutene and high-knock rating gasoline |
| CN106467449B (en) * | 2015-08-19 | 2020-05-12 | 中国石油化工股份有限公司 | Method for preparing isobutene |
| CN106467450B (en) * | 2015-08-19 | 2020-05-12 | 中国石油化工股份有限公司 | Method for preparing isobutene |
| CN107175110B (en) * | 2016-03-11 | 2020-03-31 | 中国石油化工股份有限公司 | Hydrocarbon hydrogenation catalyst containing carbon-carbon triple bond |
| CN109384638A (en) * | 2017-08-02 | 2019-02-26 | 中国石化工程建设有限公司 | A kind of four method of hydrotreating of four hydrogenation plant of carbon and carbon of richness alkynes and alkene |
| CN109485534B (en) * | 2017-09-12 | 2021-08-20 | 中国石化扬子石油化工有限公司 | Tail gas hydrogenation method for butadiene extraction device by DMF (dimethyl formamide) method |
| CN109485538B (en) * | 2017-09-13 | 2021-09-21 | 中国石油化工股份有限公司 | Selective hydrogenation method for alkyne in carbon four fraction |
| CN114478176B (en) * | 2020-10-26 | 2024-07-02 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN114478163A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Selective hydrogenation device and selective hydrogenation method for butadiene extraction tail gas |
| CN114478164B (en) * | 2020-10-26 | 2023-09-08 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN114478162B (en) * | 2020-10-26 | 2023-09-08 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| EP4238951A1 (en) | 2020-10-26 | 2023-09-06 | China Petroleum & Chemical Corporation | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| WO2006040159A1 (en) * | 2004-10-13 | 2006-04-20 | Basf Aktiengesellschaft | Selective hydrogenation catalyst |
| CN101821361A (en) * | 2008-07-17 | 2010-09-01 | Sk能源株式会社 | Process for 1,3-butadiene separation from crude C4 stream with acetylene converter |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
| CN102614870A (en) * | 2012-03-20 | 2012-08-01 | 中国平煤神马能源化工集团有限责任公司 | Vinylacetylene hydrogenation catalyst and preparation method thereof |
| CN102649660A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for removing phenylacetylene in presence of styrene |
-
2012
- 2012-10-30 CN CN201210424643.XA patent/CN103787811B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| WO2006040159A1 (en) * | 2004-10-13 | 2006-04-20 | Basf Aktiengesellschaft | Selective hydrogenation catalyst |
| CN101821361A (en) * | 2008-07-17 | 2010-09-01 | Sk能源株式会社 | Process for 1,3-butadiene separation from crude C4 stream with acetylene converter |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
| CN102649660A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for removing phenylacetylene in presence of styrene |
| CN102614870A (en) * | 2012-03-20 | 2012-08-01 | 中国平煤神马能源化工集团有限责任公司 | Vinylacetylene hydrogenation catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103787811A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103787811B (en) | A kind of method of hydrotreating of divinyl tail gas | |
| CN109678635B (en) | Saturated hydrocarbon cracking gas separation system and utilization method of ethane/propane-rich saturated hydrocarbon | |
| CN103787815B (en) | A kind of method of hydrotreating of divinyl tail gas | |
| CN1096440C (en) | Improved chemical absorption process for recovering olefins from cracked gases | |
| CN101445419B (en) | Method for separating lower hydrocarbon containing light gas by combining distillation and solvent absorption | |
| CN100473715C (en) | Process flow for raw material pretreatment portion of catalytic dry gas produced phenylethane | |
| CN101475429B (en) | Method for comprehensive utilization of cracking C4 | |
| CN105585411A (en) | Hydrogenation method of butadiene extraction tail gas | |
| CN107827698B (en) | Non-cryogenic separation method and system for ethylene-containing pyrolysis gas | |
| CN103787813B (en) | A kind of divinyl tail gas hydrogenation device and method | |
| CN104177214B (en) | A kind of catalytic cracking rich gas and methanol to olefins reaction product composite liberation method | |
| CN102041092B (en) | Method for widening catalytic reforming raw material | |
| CN103041699B (en) | Butadiene tail gas hydrogenation unit and method | |
| EP2174924A1 (en) | A separating method of cracked methanol gas to prepare polymer grade low carbon olefin | |
| CN111320524A (en) | Method and device for separating ethylene and propylene from pyrolysis gas and/or dry gas | |
| CN103041700B (en) | Butadiene tail gas hydrogenation unit and hydrogenation method | |
| CN102050695A (en) | Method for recycling waste gas of butadiene extracting device | |
| CN109485534A (en) | A kind of method of DMF method butadiene extraction device tail gas hydrogenation | |
| CN103121905B (en) | Recovery method of hydrocarbon fuel gas rich in alkyne | |
| CN112707786B (en) | Pyrolysis gas separation system and separation method | |
| CN101671221A (en) | Preparation method of polymer solvent iso-butane | |
| CN107746366A (en) | The method that isopentane is extracted from naphtha | |
| CN207749076U (en) | A kind of refinery product's upgrading synergy and hydrogen recovery system | |
| CN113354502A (en) | Method for separating low-carbon hydrocarbon from unsaturated dry gas by combined absorption and recovery | |
| CN110156557A (en) | A kind of recovery method of petrochemical industry output gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |