CN103420765A - Method for increasing butene-2 yield through C4 fraction containing small amount of butadiene - Google Patents
Method for increasing butene-2 yield through C4 fraction containing small amount of butadiene Download PDFInfo
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- CN103420765A CN103420765A CN2012101504675A CN201210150467A CN103420765A CN 103420765 A CN103420765 A CN 103420765A CN 2012101504675 A CN2012101504675 A CN 2012101504675A CN 201210150467 A CN201210150467 A CN 201210150467A CN 103420765 A CN103420765 A CN 103420765A
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- divinyl
- butene
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Abstract
The present invention relates to a method for increasing a butene-2 yield through a C4 fraction containing a small amount of butadiene, wherein the technical problem of low olefin yield in the prior art is mainly solved with the present invention. The technical scheme comprise that a C4 fraction containing a small amount of butadiene and hydrogen are adopted as raw materials, and the raw materials contact a catalyst at a reactor inlet temperature of 30-70 DEG C under a pressure of 1.2-2 MPa according to a hydrogen/butadiene ratio of 2.0-3.0, wherein the catalyst is a nickel base catalyst. With the technical scheme, the problem in the prior art is well solved, and the method can be widely used for olefin disproportionation, alkylation and other industrial productions.
Description
Technical field
The present invention relates to a kind of method of the volume increase of the C-4-fraction containing a small amount of divinyl butene-2.
Background technology
The industry C-4-fraction mainly contains cracking of ethylene by-product carbon this and refinery's by-product carbon four, the divinyl that the quantity that contains these carbon four does not wait, n-butene (butene-1, butene-2), iso-butylene, Trimethylmethane, normal butane etc., these components are all broad-spectrum industrial chemicals, a large amount of C 4 olefins that particularly wherein contain.Because carbon fourth class residue cut after carbon four, refinery C four and ether thereof after one-stage hydrogenation carbon four, secondary hydrogenation carbon four, general carbon-4 and ether thereof all contains a certain amount of alkynes, diolefine etc., affect to some extent the purity of downstream process and product, in some polyreaction requirement raw material olefin, alkynes and diolefine are less than 1 * 10
-6.Therefore selective hydrogenation catalyst is proposed to very high requirement: catalyzer has good selectivity, only alkynes and diene hydrogenation is not lost to monoolefine; Catalyzer has good activity, at lower temperature, reacts, and reduces and by olefin oligomerization, catalyzer is polluted, and cause catalyst deactivation; Catalyzer has longer regeneration period and life-span.In addition, as olefin disproportionation or cracking propylene enhancing, these Technologies increase day by day to the demand containing the high-quality butene-2 material of divinyl not, are badly in need of meeting selecting hydrogenation to remove diolefine and the hydro-isomerization conversion butene-1 compounding technology to butene-2.The SHP technique of UOP (UOP) (
Oil Gas J, 1988,
86(49): 40～43) adopt noble metal catalyst.Although butadiene conversion is up to 99.8%, the butene-1 isomerization rate reaches 76.1%, and the normal butane growing amount reaches 35.7%.
Recently, IFP develops LD-267R catalyzer (NPRA, 2001.AM-01-51), for refinery C four hydro-isomerization industrialization data, shows butadiene conversion～100%, product 2-Butene/1-Butene mass percent is～2.0, n-butene selectivity～98.0%.Northization institute has developed the BC-H-40 catalyzer, selects diolefine and alkynes in the hydrogenation and removing C-4-fraction, and after hydrogenation, the diolefine massfraction is less than 1 * 10
-6, the butene-1 yield can reach 97-99%; The selective hydrogenation catalyst QSH-01 of Shandong institute exploitation, can drop to the diolefine massfraction in raw material below 0.005%, and the monoolefine yield is more than 100%, and the butene-1 isomerization rate is more than 60%.And the present invention adopts nickel-base catalyst, reduced the catalyzer cost, green oil generates few, and regeneration period and catalyst life are long; Divinyl is all selected hydrogenation, and olefin yields is more than 98.5%; The molecular balance index is more than 94%.
Summary of the invention
Technical problem to be solved by this invention is the technical problem that the butene-1 isomerization rate is low, olefin yields is low existed in prior art.Provide a kind of new carbon containing a small amount of divinyl four to increase production the method for butene-2s, the method has advantages of that the butene-1 isomerization rate is high, olefin yields is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of the volume increase of the C-4-fraction containing a small amount of divinyl butene-2, C-4-fraction and the hydrogen that contains a small amount of divinyl of take is raw material, at reactor inlet temperature 30 ~ 70
oC, pressure 1.2 ~ 2MPa, under the condition of hydrogen/divinyl 2.0 ~ 3.0, raw material contacts with catalyzer, and described catalyzer by weight percentage, comprises following component: (a) 15 ~ 20% metallic nickel or its oxide compound; (b) 0 ~ 6.0% be selected from least one element or its oxide compound in rare earth; (c) 0 ~ 2.0% be selected from the periodic table of elements
At least one element in A or its oxide compound; (d) 0 ~ 12.0% be selected from least one element or its oxide compound in silicon, phosphorus, boron or fluorine; (e) 0 ~ 10.0% be selected from the element of at least one in IVB or its oxide compound in the periodic table of elements; (f) 20 ~ 85% alumina catalyst supports.
In technique scheme, the C-4-fraction preferred version is to derive from carbon four after ethylene plant's ether, carbon-4 or select one or more the mixture in hydrogenating carbon four, plant catalytic cracking C-4-fraction, described carbon four hydrocarbon feed compositions are for containing Trimethylmethane, normal butane, anti-butene-2, butene-1, iso-butylene, maleic-2 and a small amount of divinyl, especially, the sulfocompound that contains a small amount of thiomethyl alcohol, hydrogen sulfide in carbon four hydrocarbon chargings.In described C-4-fraction, the content of divinyl is counted and is less than 2.0% and be greater than zero with material carbon quadruple amount per-cent.The preferred described catalyzer of technical scheme by weight percentage, also comprises 0.5 ~ 5.0% sulphur or its compound; The mol ratio preferable range of reacting required hydrogen/divinyl is 2.15 ~ 2.8; The pressure preferable range of reacting required is 1.2 ~ 1.6MPa, and the temperature preferable range is 40 ~ 70
oC.
Nickel catalyzator has the character of better anti-impurity and poisonous substance than palladium catalyst, especially to sulfocompound, there is adaptability preferably, raw material is after the catalyzer contact, divinyl 100% hydrocracking, contain the butene-1 and the butene-2 that basically are equivalent to the thermodynamic(al)equilibrium ratio in reaction effluent; For hydroisomerization reactor, use technical scheme of the present invention, can effectively reduce the alkene loss, guarantee higher butene-1 isomerization rate to have obtained technique effect preferably simultaneously.
The calculation formula related in reaction is as follows:
Below by embodiment, the invention will be further elaborated, but these embodiment in no case are construed as limiting scope of the present invention.
Embodiment
[embodiment 1]
Carry out hydrogenation and isomerization operation in fixed bed adiabatic reactor.Load the nickel-base catalyst that according to claim 2 prepared by method in reactor, this catalyzer carries out vulcanization in situ and activation.The selection hydrogenation of C 4 fraction and isomerization operation after the ether that to contain in a continuous manner the divinyl massfraction be 1.56%.
In hydroisomerization process, operational condition is as follows: reactor inlet temperature: 60
oC; Reactor pressure: 1.2MPa
Liquid phase air speed: 6h
-1, hydrogen/divinyl mol ratio: 2.15; The composition of the hydroisomerization reactor effluent operated under material and above-mentioned condition is in Table 1.
Table 1
[embodiment 2]
Carry out hydrogenation and isomerization operation in fixed bed adiabatic reactor.Load the nickel-base catalyst that according to claim 2 prepared by method in reactor, this catalyzer carries out vulcanization in situ and activation.Contain in a continuous manner the divinyl massfraction and be 0.60% the selection hydrogenation of taking out remaining C 4 fraction and isomerization operation.
In hydroisomerization process, operational condition is as follows: reactor inlet temperature: 60
oC; Reactor pressure: 1.4MPa; Liquid phase air speed: 6h
-1Hydrogen/divinyl mol ratio: 2.67; The composition of the hydroisomerization reactor effluent operated under material and above-mentioned condition forms in Table 2.
Table 2
[embodiment 3]
Carry out hydrogenation and isomerization operation in fixed bed adiabatic reactor.Load the nickel-base catalyst that according to claim 2 prepared by method in reactor, this catalyzer carries out vulcanization in situ and activation.The selection hydrogenation of carbon four C 4 fractions and isomerization operation after the ether that to contain in a continuous manner the divinyl massfraction be 0.21%.
The hydroisomerization operational condition is as follows: reactor inlet temperature: 70
oC; Reactor pressure: 1.6MPa; Liquid phase air speed: 6h
-1, hydrogen/divinyl mol ratio: 2.8; The composition of the hydroisomerization reactor effluent operated under material and above-mentioned condition forms in Table 3.
Table 3
[Comparative Examples 1]
Carry out hydrogenation and isomerization operation in fixed bed adiabatic reactor.Filling commodity Pd/Al in reactor
2O
3Catalyzer (containing by weight percentage 0.25 % Pd), this catalyzer carries out with regard to activatable.Contain in a continuous manner the divinyl massfraction and be 0.60% the selection hydrogenation of taking out remaining C 4 fraction and isomerization operation.
In hydroisomerization process, operational condition is as follows: reactor inlet temperature: 60
oC; Reactor pressure: 1.6MPa;
Liquid phase air speed: 6h
-1, hydrogen/divinyl mol ratio: 2.65; The composition of the hydroisomerization reactor effluent operated under material and above-mentioned condition forms in Table 4.
Table 4
Claims (6)
1. the method containing the C-4-fraction of a small amount of divinyl volume increase butene-2, C-4-fraction and the hydrogen that contains a small amount of divinyl of take is raw material, at reactor inlet temperature 30 ~ 70
oC, pressure 1.2 ~ 2MPa, under the condition of hydrogen/divinyl 2.0 ~ 3.0, raw material contacts with catalyzer, and described catalyzer by weight percentage, comprises following component:
(a) 15 ~ 20% metallic nickel or its oxide compound;
(b) 0 ~ 6.0% be selected from least one element or its oxide compound in rare earth;
(c) 0 ~ 2.0% be selected from the periodic table of elements
At least one element in A or its oxide compound;
(d) 0 ~ 12.0% be selected from least one element or its oxide compound in silicon, phosphorus, boron or fluorine;
(e) 0 ~ 10.0% be selected from the element of at least one in IVB or its oxide compound in the periodic table of elements;
(f) 20 ~ 85% alumina catalyst supports.
2. the method for the volume increase of the C-4-fraction containing a small amount of divinyl butene-2 according to claim 1, is characterized in that described catalyzer by weight percentage, also comprises 0.5 ~ 5.0% sulphur or its compound.
3. the method for the volume increase of the C-4-fraction containing a small amount of divinyl butene-2 according to claim 1, is characterized in that
Contain butene-1 and butene-2 and divinyl in described C-4-fraction, the content of divinyl is counted and is less than 2.0% and be greater than zero with material carbon quadruple amount per-cent.
4. the method for the C-4-fraction volume increase butene-2 containing a small amount of divinyl according to claim 1, the mol ratio that it is characterized in that reacting required hydrogen/divinyl is 2.15 ~ 2.8.
5. the method for the volume increase of the C-4-fraction containing a small amount of divinyl butene-2 according to claim 1, is characterized in that required pressure is 1.2 ~ 1.6MPa, and temperature is 40 ~ 70
oC.
6. according to the method containing the C-4-fraction of a small amount of divinyl volume increase butene-2 of claim 1, it is characterized in that described C-4-fraction can hang oneself carbon four after the cracking c_4 of selecting hydrogenation, ether, carbon-4 and refinery C four.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642324A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Non-noble metal selective hydrogenation catalyst, preparation method and application thereof |
| CN105709786A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of butadiene and isomerization of 1-butylene, and preparation method and application thereof |
| CN105712832B (en) * | 2014-12-04 | 2018-10-12 | 中国石油化工股份有限公司 | A method of isobutene is produced for raw material with MTO by-products carbon four |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428225A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Nickel base catalyst for producing butylene-1 with butylenes-2 hydroisomerization containing a few butadiene |
| CN101472864A (en) * | 2006-05-05 | 2009-07-01 | 国际壳牌研究有限公司 | A process for selectively hydrogenating butadiene in an C4 olefin stream containing a catalyst poison with the simultaneous isomerization of 1-butene to 2-butene |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101472864A (en) * | 2006-05-05 | 2009-07-01 | 国际壳牌研究有限公司 | A process for selectively hydrogenating butadiene in an C4 olefin stream containing a catalyst poison with the simultaneous isomerization of 1-butene to 2-butene |
| CN101428225A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Nickel base catalyst for producing butylene-1 with butylenes-2 hydroisomerization containing a few butadiene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642324A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Non-noble metal selective hydrogenation catalyst, preparation method and application thereof |
| CN105709786A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of butadiene and isomerization of 1-butylene, and preparation method and application thereof |
| CN105709786B (en) * | 2014-12-04 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of selectively hydrogenating butadiene, 1 butylene heterogeneous catalyst and its preparation method and application |
| CN105642324B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of base metal selective hydrocatalyst and its preparation method and application |
| CN105712832B (en) * | 2014-12-04 | 2018-10-12 | 中国石油化工股份有限公司 | A method of isobutene is produced for raw material with MTO by-products carbon four |
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