CN103787815A - 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: extracting butadiene tail gas, a selective hydrogenation is carried out in a one-section hydrogenation reactor, vinylacetylene is performed with hydro-conversion to 1,3-butadiene; the one-section hydrogenation reaction products are seperared, a part which is rich in 1,3-butadiene is sent to a butadiene extraction device, other part is performed with the selective hydrogenation reaction through a second-section hydrogenation reactor, alkynes and dialkene are performed with hydro-conversion to 1-butylene, two hydrogenation reaction products are sent to a recovery device of 1-butylene. The method is capable of fully recovering the valuable substances in the butadiene tail gas, and the economic benefit is obvious.
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 that these are rich in to alkynes makes full use of, will greatly improve utilization ratio and the economic benefit of hydrocarbon resources.
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 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.
In the method, the alkynes in tail gas and 1,3-butadiene are all hydrogenated to 1-butylene, are not recovered as important industrial chemicals 1,3-butadiene, and the economy that carbon four fully utilizes obviously reduces.
Another kind method is that the divinyl tail gas to being rich in alkynes is selected 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.
As everyone knows, in the c4 fraction of high concentration ethylene ethyl-acetylene (VA), ethylacetylene (EA), divinyl, hydrogenation catalyst is the highest to the activity of VA, first it is carried out to hydrogenation reaction, and after VA is almost completely by hydrogenation, EA just participates in hydrogenation reaction.If EA is also completely by hydrogenation, catalyzer just carries out hydrogenation to divinyl, causes a large amount of losses of divinyl.
In the disclosed embodiment 1 ~ 8 of CN200810239462.3, VA transformation efficiency is at 90 ~ 93%, EA transformation efficiency 100%, and the yield of 1,3-butadiene is greater than 100%, and the practical situation of this and prior art there are differences.Use prior art and catalyzer, the in the situation that of EA complete hydrogenation, divinyl loss is very large.As by VA complete hydrogenation, do not lose if control 1,3-butadiene, EA hydrogenation hardly, the concentration of importing and exporting EA in material is almost constant.Due in divinyl tail gas, EA concentration is higher, therefore use CN200810239462.3 patented technology, guaranteeing 1, when situation that 3-divinyl does not lose, in hydrogenation products, EA concentration is higher, and this material send butadiene extraction unit to make raw material, can be larger to two extraction systematic influences, increase operational load and the energy consumption of tower.
Summary of the invention
In order fully to recycle divinyl tail gas, overcome the higher problems such as large or 1,3-butadiene loss is larger to Butadiene Extraction systematic influence of EA concentration that reclaim in prior art in 1,3-butadiene, with the problem such as 1-butylene output is not high, the invention provides a kind of divinyl tail gas hydrogenation method.
The method of hydrotreating of a kind of divinyl tail gas provided by the invention is achieved in that
A method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
(1) from the divinyl tail gas of butadiene extraction unit, after mixing with liquid phase from one-stage hydrogenation reactor outlet separating tank and a section feeding hydrogen after liquefaction, enter one-stage hydrogenation reactor top, carry out selective hydrogenation reaction; Reaction product enters one-stage hydrogenation reaction outlet separating tank after cooling, the tank deck non-condensable gas carrying device that described one-stage hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtaining, a part is circulated to one-stage hydrogenation reactor inlet, and rest part enters butadiene recovery column;
Described one-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described selective hydrogenation reaction: to be selected from one or more in aluminum oxide, gac, carbon black, zeolite, molecular sieve, silicon oxide as carrier, take palladium as active ingredient, being selected from Bi, Sb, Pb, In, be different from one or more in the VIII family element, IB family element, rare earth element, alkali metal, alkali earth metal, halogens of palladium as modified component; Described active ingredient accounts for 0.01 ~ 50% of described catalyst weight, and described modified component accounts for 0.1 ~ 20% of described catalyst weight;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 ℃, and pressure is 1.0 ~ 3.0MPa, and in the mixture that enters described hydrogenator, the mol ratio of hydrogen and vinylacetylene is 1 ~ 5, and recycle feed volume ratio is 10 ~ 30; Described recycle feed volume ratio be the inventory that is circulated to one-stage hydrogenation reactor inlet from described one-stage hydrogenation reaction outlet separating tank with described liquefaction the ratio of divinyl tail gas inventory;
(2) react from described one-stage hydrogenation the liquid phase rectifying in described butadiene recovery column that exports separating tank; The top gaseous phase overhead product of described butadiene recovery column is after overcooling, gas-liquid separation, what obtain is main containing 1, the liquid phase material of 3-divinyl send butadiene extraction unit, the non-condensable gas discharger obtaining, and the tower reactor material of described butadiene recovery column enters second-stage hydrogenation reactor after boosting;
The working pressure of described butadiene recovery column is 0.3 ~ 0.8MPa, and reflux ratio is 10 ~ 30;
(3) after mixing from the tower reactor material of described butadiene recovery column and the liquid phase of secondary hydrogenation reaction outlet separating tank and two section feeding hydrogen, enter second-stage hydrogenation reactor top, carry out hydrogenation reaction; Described hydrogenation reaction product enters described second-stage hydrogenation reactor outlet separating tank after being cooled to 30 ~ 50 ℃, the tank deck non-condensable gas carrying device that described secondary hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtaining, a part is circulated to second-stage hydrogenation reactor entrance, and rest part send 1-butylene tripping device to reclaim 1-butylene;
Described second-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described hydrogenation reaction: take pseudo-boehmite as carrier; In catalyzer, contain nickel, molybdenum, zinc, described nickel account for total catalyst weight 10 ~ 40%, described molybdenum account for total catalyst weight 0.5 ~ 3%, described zinc accounts for 0.5 ~ 3% of total catalyst weight; Described catalyzer also contains IA family element, and described IA family element accounts for 0.1 ~ 5% of total catalyst weight;
The condition of described hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 ℃, and pressure is 1.0 ~ 3.0MPa, and the mol ratio that enters hydrogen and alkynes in the mixture of described hydrogenator, diolefine is 1 ~ 5, and recycle feed volume ratio is 20 ~ 60.
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), selective hydrogenation reaction can be selected hydrogenation catalyst well known in the prior art, for example, in CN102249838, CN102249834 disclosed selective acetylene hydrocarbon hydrogenation catalyst, catalyzer is using aluminum oxide as carrier, take palladium as active ingredient, take Ag, Mg, K as modified component; Described active component palladium accounts for 0.1 ~ 10% of described catalyst weight, and described modified component Ag, Mg, K account for 0.01 ~ 10%, 0.01 ~ 5%, 0.01 ~ 2% of described catalyst weight; Account for 2 ~ 4% of described catalyst weight at active component palladium described in preferred catalyzer, described modified component Ag, Mg, K account for 1 ~ 2%, 1 ~ 3%, 0.03 ~ 1% of described catalyst weight.
The condition of described selective hydrogenation reaction is: reactor inlet temperature is that 30 ~ 60 ℃, pressure are 1.2 ~ 2.0MPa, preferably 35 ~ 50 ℃, 1.4 ~ 1.6MPa; For guaranteeing that catalyzer has good selectivity, control and reduce reacting of 1,3-butadiene and hydrogen, hydrogen: the mol ratio of vinylacetylene is controlled at 1 ~ 1.5, preferably 1 ~ 1.2; Due in first stage reactor, vinylacetylene per pass conversion is not high, and recycle stock can be controlled on the one hand the temperature rise of reactor, can improve on the other hand the total transformation efficiency of vinylacetylene, and recycle ratio is 15 ~ 25, and preferably 17 ~ 23.
Generate 1,3-butadiene at one-stage hydrogenation reactor medium vinyl acetylene selective hydrogenation, its per pass conversion is not less than 50%, and 1,3-butadiene does not lose and has an increase; A liquid phase part for one-stage hydrogenation reactor outlet separating tank bottom is circulated to first stage reactor entrance, and the total conversion rate that generates 1,3-butadiene at first stage reactor medium vinyl acetylene selective hydrogenation is greater than 95%.
In the specific implementation, in step (2), the operational condition of rectifying is: working pressure 0.4 ~ 0.6MPa, reflux ratio 18 ~ 23.
By rectifying, obtain being rich in the liquid phase material of 1,3-butadiene in this column overhead, wherein the total content of vinylacetylene and ethylacetylene is less than 3%, and 1,3-butadiene content is greater than 90%; This material is as the raw material of butadiene extraction unit.
In the specific implementation, in step (3), alkynes, the whole selective hydrogenations of diolefine are converted into 1-butylene and 2-butylene, and hydrogenation reaction can be selected hydrogenation catalyst well known in the prior art, for example disclosed selective hydrogenation catalyst in CN200910080849.3.Hydrogenation catalyst is take pseudo-boehmite as carrier; In described catalyst for hydrogenation, contain nickel, molybdenum, zinc and silicon, described nickel, molybdenum, zinc and silicon account for respectively 15 ~ 35%, 1 ~ 2%, 1 ~ 2%, 1.2 ~ 4% of total catalyst weight, and preferably 20 ~ 30%, 1.2 ~ 1.8%, 1.2 ~ 1.6%, 1.5 ~ 3%;
The condition of described hydrogenation reaction is: reactor inlet temperature is 20 ~ 60 ℃, pressure is 1.2 ~ 2.5MPa, the mol ratio of hydrogen and alkynes, diolefine is 1.1 ~ 3, recycle feed volume ratio is 25 ~ 50, preferred hydrogenation operation condition is: reactor inlet temperature is 30 ~ 50 ℃, pressure is 1.3 ~ 1.6MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.2 ~ 1.4, and recycle feed volume ratio is 30 ~ 45.
In secondary hydrogenation reaction, 1,3-divinyl, 1,2-divinyl, vinylacetylene, ethylacetylene selective hydrogenation generate butene-1 and butene-2, transformation efficiency is 100%, in reactor outlet material, alkynes, diene content are less than 10ppm, and this material can be used as the raw material of butene-1 retrieving arrangement.
The tail gas that is rich in alkynes that the present invention discharges take butadiene extraction unit, as raw material, carries out selective hydrogenation at first stage reactor, is 1,3-butadiene by the vinylacetylene hydrocracking in tail gas.Hydrogenation products enters butadiene recovery column, obtains being rich in the material of 1,3-butadiene by rectifying from tower top, and this material 1,3-butadiene content is high, and vinylacetylene, ethylacetylene content are very low, is suitable as the raw material of butadiene extraction unit.Butadiene recovery column still material is mainly containing 1-butylene, 2-butylene, ethylacetylene, 1,2-divinyl, 1,3-divinyl, after this material pressurization, deliver to second stage reactor, alkynes, diolefine selective hydrogenation are converted into 1-butylene, reaction product is rich in 1-butylene, and this material can be used as the raw material of 1-butylene retrieving arrangement to reclaim 1-butylene.The method had both increased the output of 1.3-divinyl and 1-butylene, had reduced again load and the energy consumption of butadiene extraction unit, and divinyl tail gas is fully used, remarkable in economical benefits.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of divinyl waste gas utilization method of the present invention.
Nomenclature:
The divinyl tail gas of 1 liquefaction; 2 one sections of hydrogen feed; 3 one-stage hydrogenation reactors; 4 one-stage hydrogenation reactor products; 5 one section outlet water coolers; 6 one section outlet separating tanks; 7 non-condensable gases; 8 one sections of recycle pumps; 9 one sections of circulation fluids; 10 one section outlet separating tanks go the liquid phase of butadiene recovery column; 11 butadiene recovery column; 12 condensers; 13 return tanks; 14 non-condensable gases; 15 reflux pumps; 1,3-butadiene material is rich on 16 butadiene recovery column tops; 17 butadiene recovery column still materials; 18 19 2 sections of second stage reactor fresh feed pumps hydrogen feed; 20 second-stage hydrogenation reactor chargings; 21 second-stage hydrogenation reactors; 22 second-stage hydrogenation reactor products; 23 second stage exit water coolers; 24 second stage exit separating tanks; 25 non-condensable gases; 26 are rich in 1-butylene material; 27 2 sections of circulation fluids; 28 2 sections of recycle pumps
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
The divinyl tail gas 1 having liquefied from butadiene extraction unit, 30 ℃ of temperature, flow 1000kg/h, the 20000kg/h liquid phase 9 and the 22kg/h hydrogen 2 that come with second stage exit separating tank mix, and enter from the top of first stage reactor 3.The entry condition of first stage reactor is: 40 ℃ of temperature, pressure 1.5MPa, the mol ratio of hydrogen and divinyl tail gas 1 medium vinyl acetylene in hydrogen/vinylacetylene mol ratio 1.03:1(hydrogen 2), one section of reaction product 4 enters water cooler 5, with water cooling laggard enter one section outlet separating tank 6, a liquid phase part is mixed with divinyl tail gas 1 after recycle pump 8 boosts, another liquid phase material 10 enters butadiene recovery column middle part, non-condensable gas 7 dischargers of tank top.In butadiene recovery column 11, top gaseous phase is delivered to return tank 13 after entering condenser 12 use water coolings, non-condensable gas 14 dischargers, phlegma is the C-4-fraction that is rich in 1,3-butadiene, and a part is delivered to trim the top of column with reflux pump 15, another part 16 send butadiene extraction unit to make raw material, this gang of mass flow 748.9kg/h, 1,3-butadiene content is 94.42mol%.After 17 use pump 18 pressurizations of tower reactor material, mix with liquid phase 27 and the hydrogen 19 of second stage exit separating tank 24, enter from second stage reactor 21 tops.Hydrogen 19 flows are 10.5kg/h, circulation fluid 27 flow 10000kg/h.The entry condition of second stage reactor is: 42 ℃ of temperature, pressure 1.5MPa, hydrogen in hydrogen/(alkynes+diolefine) mol ratio 1.14:1(hydrogen 19: alkynes and diolefine sum in butadiene recovery column still 17).Second stage exit material 22 is water-cooled to 43 ℃ in second stage exit water cooler 23 use, enter into second stage exit separating tank 24, non-condensable gas 25 carrying devices, liquid phase is the material that is rich in 1-butylene, after a part 27 use pump 28 pressurizations, be circulated to two sections of entrances, another part 26 is delivered to 1-butylene retrieving arrangement to reclaim 1-butylene, this gang of material 26 flow 234kg/h, 1-butylene content 55.23mol%.
The catalyzer that one-stage hydrogenation uses is using aluminum oxide as carrier, take palladium as active ingredient, take Ag, Mg, K as modified component; Palladium accounts for 3% of described catalyst weight, and modified component Ag, Mg, K account for 1.5%, 2%, 0.05% of described catalyst weight; One-stage hydrogenation reactor inlet temperature is 40 ℃, and pressure is 1.5MPa, and in one-stage hydrogenation reactor inlet material, the mol ratio of hydrogen and vinylacetylene is 1.03:1, and one section of recycle feed volume ratio is 20; In one-stage hydrogenation reactor, the total conversion rate of vinylacetylene is 96.25%, and in divinyl tail gas (logistics 1), the content of 1,3-butadiene is 40.99%, and after reaction, in first stage reactor outlet logistics 4, the content of 1,3-butadiene is increased to 76.9%.
The working pressure of butadiene recovery column is 0.65MPaG, and reflux ratio is 20.Through rectifying separation, the liquid phase material that is rich in 1,3-butadiene 16 obtaining from tower top, wherein the content of 1,3-butadiene is 94.42%, the total content low (being 1.29%) of vinylacetylene and ethylacetylene, and this material is suitable as the raw material of butadiene extraction unit.The material 17 obtaining from tower reactor, the content of 1,3-butadiene, 1，2-butadiene, ethylacetylene, vinylacetylene higher (being 81.99%), this material be applicable to doing further selection hydrogenation generate butene-1 raw material.The catalyzer that secondary hydrogenation uses, take pseudo-boehmite as carrier, contains nickel, molybdenum, zinc and silicon in catalyzer, nickel accounts for 25% of total catalyst weight, and molybdenum accounts for 1.5% of total catalyst weight, and zinc accounts for 1.4% of total catalyst weight, and silicon accounts for 2% of total catalyst weight.Second-stage hydrogenation reactor temperature in is 42 ℃, and pressure is 1.5MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.26:1, and two sections of recycle feed volume ratios are 44.In second-stage hydrogenation reactor, the total conversion rate of alkynes, diolefine is 100%, and the selectivity that generates butene-1 is high.In the charging (logistics 17) of second stage reactor, alkynes, diene content are 81.99%, and butene-1 content is 0.16%.After reaction, in second stage reactor outlet logistics 26, not containing alkynes, diolefine, butene-1 content is increased to 55.23%.This logistics is suitable as the raw material of butene-1 retrieving arrangement.
The quality group prejudice table 1 of each main streams.
Table 1
Continued 1
Claims (7)
1. a method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
(1) from the divinyl tail gas of butadiene extraction unit, after mixing with liquid phase from one-stage hydrogenation reactor outlet separating tank and a section feeding hydrogen after liquefaction, enter one-stage hydrogenation reactor top, carry out selective hydrogenation reaction; Reaction product enters one-stage hydrogenation reaction outlet separating tank after cooling, the tank deck non-condensable gas carrying device that described one-stage hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtaining, a part is circulated to one-stage hydrogenation reactor inlet, and rest part enters butadiene recovery column;
Described one-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described selective hydrogenation reaction: to be selected from one or more in aluminum oxide, gac, carbon black, zeolite, molecular sieve and silicon oxide as carrier, take palladium as active ingredient, being selected from Bi, Sb, Pb, In, be different from one or more in VIII family element, IB family element, rare earth element, alkali metal, alkali earth metal and the halogens of palladium as modified component; Described active ingredient accounts for 0.01 ~ 50% of described catalyst weight, and described modified component accounts for 0.1 ~ 20% of described catalyst weight;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 ℃, and pressure is 1.0 ~ 3.0MPa, and in the mixture that enters described hydrogenator, the mol ratio of hydrogen and vinylacetylene is 1 ~ 5, and recycle feed volume ratio is 10 ~ 30; Described recycle feed volume ratio be the inventory that is circulated to one-stage hydrogenation reactor inlet from described one-stage hydrogenation reaction outlet separating tank with described liquefaction the ratio of divinyl tail gas inventory;
(2) react from described one-stage hydrogenation the liquid phase rectifying in described butadiene recovery column that exports separating tank; The top gaseous phase overhead product of described butadiene recovery column is after overcooling, gas-liquid separation, what obtain is main containing 1, the liquid phase material of 3-divinyl send butadiene extraction unit, the non-condensable gas discharger obtaining, and the tower reactor material of described butadiene recovery column enters second-stage hydrogenation reactor after boosting;
The working pressure of described butadiene recovery column is 0.3 ~ 0.8MPa, and reflux ratio is 10 ~ 30;
(3) after mixing from the tower reactor material of described butadiene recovery column and the liquid phase of secondary hydrogenation reaction outlet separating tank and two section feeding hydrogen, enter second-stage hydrogenation reactor top, carry out hydrogenation reaction; Described hydrogenation reaction product enters described second-stage hydrogenation reactor outlet separating tank after being cooled to 30 ~ 50 ℃, the tank deck non-condensable gas carrying device that described secondary hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtaining, a part is circulated to second-stage hydrogenation reactor entrance, and rest part send 1-butylene tripping device to reclaim 1-butylene;
Described second-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described hydrogenation reaction: take pseudo-boehmite as carrier; In catalyzer, contain nickel, molybdenum, zinc, described nickel account for total catalyst weight 10 ~ 40%, described molybdenum account for total catalyst weight 0.5 ~ 3%, described zinc accounts for 0.5 ~ 3% of total catalyst weight; Described catalyzer also contains IA family element, and described IA family element accounts for 0.1 ~ 5% of total catalyst weight;
The condition of described hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 ℃, and pressure is 1.0 ~ 3.0MPa, and the mol ratio that enters hydrogen and alkynes in the mixture of described hydrogenator, diolefine is 1 ~ 5, and recycle feed volume ratio is 20 ~ 60; Described recycle feed volume ratio is to be circulated to the inventory of second-stage hydrogenation reactor entrance and the ratio that enters second stage reactor inventory from butadiene recovery column still from described second-stage hydrogenation reactor outlet separating tank.
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 selective hydrogenation catalyst is using aluminum oxide as carrier, take palladium as active ingredient, take Ag, Mg and K as modified component; Described active component palladium accounts for 0.1 ~ 10% of catalyst weight, and described modified component Ag, Mg, K account for respectively 0.01 ~ 10%, 0.01 ~ 5%, 0.01 ~ 2% of catalyst weight;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 30 ~ 60 ℃, and pressure is 1.2 ~ 2.0MPa, and the mol ratio of described hydrogen and vinylacetylene is 1 ~ 1.5, and recycle feed volume ratio is 15 ~ 25.
4. method of hydrotreating according to claim 3, is characterized in that:
Described active component palladium accounts for 2 ~ 4% of described catalyst weight, and described modified component Ag, Mg, K account for respectively 1 ~ 2%, 1 ~ 3%, 0.03 ~ 1% of described catalyst weight;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 35 ~ 50 ℃, and pressure is 1.4 ~ 1.6MPa, and the mol ratio of described hydrogen and vinylacetylene is 1 ~ 1.2, and recycle feed volume ratio is 17 ~ 23.
5. method of hydrotreating according to claim 1, is characterized in that:
In step (2), the working pressure of described butadiene recovery column is 0.4 ~ 0.6MPa, and reflux ratio is 18 ~ 23.
6. method of hydrotreating according to claim 1, is characterized in that:
In step (3), in described catalyst for hydrogenation, contain nickel, molybdenum, zinc and silicon, described nickel, molybdenum, zinc and silicon account for respectively 15 ~ 35%, 1 ~ 2%, 1 ~ 2%, 1.2 ~ 4% of total catalyst weight;
The condition of described hydrogenation reaction is: reactor inlet temperature is 20 ~ 60 ℃, and pressure is 1.2 ~ 2.5MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.1 ~ 3, and recycle feed volume ratio is 25 ~ 50.
7. method of hydrotreating according to claim 6, is characterized in that:
Described nickel, molybdenum, zinc and silicon account for respectively 20 ~ 30%, 1.2 ~ 1.8%, 1.2 ~ 1.6%, 1.5 ~ 3% of total catalyst weight;
The condition of described hydrogenation reaction is: reactor inlet temperature is 30 ~ 50 ℃, and pressure is 1.3 ~ 1.6MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.2 ~ 1.4, and recycle feed volume ratio is 30 ~ 45.
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| CN105585411A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation method of butadiene extraction tail gas |
| WO2017170421A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Hydrogenation method |
| CN108927173A (en) * | 2018-08-06 | 2018-12-04 | 沈阳沈科姆科技有限公司 | A kind of alkynes selective hydrocatalyst and its preparation method and application |
| CN109265306A (en) * | 2017-07-17 | 2019-01-25 | 中国石化工程建设有限公司 | A kind of carbon four adds four method of hydrotreating of process units and carbon of hydrogen |
| CN109485536A (en) * | 2017-09-13 | 2019-03-19 | 中国石油化工股份有限公司 | The selection method of hydrotreating of alkynes and/or alkadienes in C-4-fraction |
| 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 |
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| CN114478164A (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 |
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