CN104945228A - Method for preparing MTBE or isobutylene by adopting mixed butane - Google Patents
Method for preparing MTBE or isobutylene by adopting mixed butane Download PDFInfo
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Abstract
The invention firstly provides a method for preparing MTBE by adopting mixed butane. The method for preparing MTBE by adopting the mixed butane comprises the following steps: A, carrying out primary hydrogenation for removing unsaturated hydrogen in the mixed butane; B, carrying out secondary hydrogenation for removing sulphur and/or nitrogen impurities in a product obtained in the step A; C, dehydrogenating a product obtained in the step B and converting the product obtained in the step B into n-butene and isobutene; D, isomerising: introducing a product obtained in the step C into an isomerising device, so that n-butene in the isomerising device is isomerised into isobutene; and E, etherifying, namely introducing a product obtained in the step D into an etherifying device, wherein isobutene in the etherifying device reacts with methyl alcohol to generate MTBE. The invention also provides a method for preparing isobutene by adopting the mixed butane. The method for preparing the isobutene by adopting the mixed butane comprises the following steps: firstly preparing MTBE by adopting any one method, and then cracking the obtained MTBE to obtain isobutene. The method for preparing MTBE or isobutylene by adopting mixed butane has the advantages that comprehensive utilization rate of the mixed butane is high, additional value of the mixed butane is greatly improved and yield of MTBE and/or isobutylene is high.
Description
Technical field
The present invention relates to a kind of method that mixed c 4 alkane prepares MTBE and/or iso-butylene.
Background technology
Iso-butylene is one of important basic chemical raw materials, be mainly used in the production of methyl tertiary-butyl ether (MTBE), polyisobutene etc., iso-butylene is also the main raw material of synthetic rubber as isoprene-isobutylene rubber, and iso-butylene or multiple Organic Chemicals are as the raw material of the trimethyl carbinol, methacrylonitrile, oxidation inhibitor etc. simultaneously.Iso-butylene is mainly derived from the mixed c 4 of steam cracking device and refinery catalytic cracking device (FCC).The method that isobutylene separation is most widely used from mixed c 4 is at present etherification technology, can synthesize MTBE on the one hand, on the other hand can by the cracking of MTBE for highly purified iso-butylene.
Mixed c 4 is steam cracking device, catalytic cracking unit and carbon four one of Main By product of deep processing device.Because of the difference of raw material, reaction depth and catalyzer, the composition comparison in difference of mixed c 4 is obvious.Under normal circumstances, mixed c 4 composition (weight) of steam cracking device by-product is about: alkane: 3%, iso-butylene: 22%, butene-1: 14%, butene-2: 11%, divinyl: 50%.Mixed c 4 composition (weight) of catalytic cracking unit by-product is about: Trimethylmethane: 34%, normal butane: 10%, iso-butylene: 15%, butene-1: 13%, butene-2: 28%.From total amount, generally the mixed c 4 of catalytic cracking unit by-product is approximately the 9%-12%(weight of device fresh feed), and the mixed c 4 of steam cracking device by-product is approximately the 40-50wt% of ethene ability.At present, the divinyl in mixed c 4, iso-butylene major part are separated, and their added value is utilized preferably, and remaining mixed c 4 alkane is used as liquefied gas as fuel by major part, and added value is lower.In addition, carbon four deep processing technology, as technique also a large amount of butanes of by-product such as isoprene-isobutylene rubber synthesis, methyl methacrylate synthesis, if continued deep processing and utilization, can improve the utilising efficiency of carbon four resource effectively.
At present, China crude refining device, steam cracking device, cat-cracker and carbon four deep processing device is building or in planning construction, scale is considerable.Therefore, following will have a large amount of mixed c 4 alkane to occur, the comprehensive utilization ratio and its chemical utilization value that how to improve mixed c 4 alkane have great realistic meaning.
Document DE102008007081 describes a kind of method extracted iso-butylene and produce n-butene oligopolymer from mixed c 4.First from carbon four mixing raw material, extracting extracts divinyl, carbon four compound 8 after extraction isolates iso-butylene with methyl alcohol by ether-based device G, then remaining carbon four compound 9 is divided into low boiling mixture (10 and 11) and high boiling mixture 14 two portions in rectification cell H: low boiling mixture is mainly n-butene (butene-1) and Trimethylmethane, and high boiling mixture is mainly normal butane and butene-2.First in I unit, selective hydrogenation is carried out to low boiling mixture, removing diene wherein, n-butene and Trimethylmethane is obtained again by rectifying separation, then n-butene separation obtained and high boiling mixture 14 merge, mixture after being finally combined carries out copolyreaction, makes the n-butene in mixture form n-butene oligopolymer.This method make use of divinyl, iso-butylene and n-butene in mixed c 4, but remaining butane is not fully utilized, and overall utilising efficiency is not very high.
Summary of the invention
Technical problem to be solved by this invention is the problem that the overall utilising efficiency of mixed c 4 alkane is not high, mixed c 4 alkane added value is low of prior art Crude Oil refining plant, steam cracking device, catalytic cracking unit or carbon four deep processing device by-product, provides a kind of method of being produced MTBE and/or iso-butylene by mixed c 4 alkane newly.Present method takes full advantage of each component in mixed c 4 alkane, makes it to be converted into MTBE and/or iso-butylene, improves the ultimate production of MTBE and/or iso-butylene.Present method has that mixed c 4 alkane comprehensive utilization ratio is high, MTBE and/or iso-butylene yield is high and mixed c 4 alkane added value obtains the advantage of larger raising.
Therefore, the invention provides a kind of method that mixed c 4 alkane prepares MTBE, comprise the following steps, steps A, first paragraph hydrogenation: to remove the unsaturated hydrocarbons in described mixed c 4 alkane; Step B, second segment hydrogenation: with the sulfur impurity in removing step A product and/or nitrogen; Step C, dehydrogenation: the product dehydrogenation of step B is converted into n-butene and iso-butylene; Step D, isomerization: the product of step C is passed into isomerization unit, makes n-butene wherein tautomerize to iso-butylene; Step e, etherificate: the product of step D is passed into ether-based device, iso-butylene wherein and methyl alcohol react and generate described MTBE.
In the present invention, term n-butene refers to butene-1, and does not comprise butene-2.In fact, also can generate a small amount of butene-2 in dehydrogenation step C in the present invention, but less and not design independently processing unit for butene-2 because of its amount.
In a kind of embodiment of the present invention, the butane content in described mixed c 4 alkane is more than 50wt%, preferred more than 65wt%, more preferably more than 80wt%.When the butane content in mixed c 4 alkane is 80 ~ 90wt%, uses the method for the invention that each component in mixed c 4 alkane can be made all to be fully utilized, thus significantly improve its added value.
In a kind of embodiment of the present invention, also comprise and the leftover materials after the etherificate comprising butane and C 4 olefin returned in steps A and/or step B and make it as the raw material of the described MTBE of preparation.Or provide heat by the leftover materials burning after the etherificate comprising butane and C 4 olefin thus for any one or more reactors in steps A ~ D.Or using the raw material of the leftover materials after the etherificate comprising butane and C 4 olefin as steam cracking device.
In a kind of embodiment, described mixed c 4 alkane comes from crude refining device, steam cracking device, catalytic cracking unit and/or carbon four mixed c 4 by product of deep processing device.
In the present invention, preferably, the catalyzer used in steps A is alumina load metallic nickel, zinc and/or palladium, the catalyzer used in step B is alumina load metal molybdenum, cobalt and/or nickel, the catalyzer used in step C is alumina load metal platinum, tin and/or zinc, the catalyzer used in step D be selected from SAPO, ZSM of modification and zeolite molecular sieve one or more, the catalyzer used in step e be selected from macropore strong acid cation exchange resin, ZSM-5 molecular sieve and heteropolyacid one or more.And step C such as carries out in moving-bed, fluidized-bed or fixed-bed reactor, step D such as carries out in fixed-bed reactor or fluidized-bed reactor, and step e is carried out in catalytic distillation reactor.
The present invention also provides a kind of mixed c 4 alkane to prepare the method for iso-butylene, comprises and first prepares MTBE with as above any one method, more described MTBE cracking is obtained described iso-butylene.The iso-butylene that in the present invention, method obtains is used to be high-purity iso-butylene.In the present invention, described MTBE cracking is such as carried out in fixed bed reaction bed, and cracking catalyzer is preferably the acid catalysts of alumina load.
The present invention, by hydrogen addition technology, De-hydrogen Technology, isomerization technique and etherification technology, makes the normal butane in mixed c 4 alkane and Trimethylmethane major part be converted into MTBE and/or iso-butylene.Remaining alkane can process preparation MTBE and/or iso-butylene further, or provides heat for hydrogenator, dehydrogenation reactor and isomerization reactor, or as steam cracking device raw material.Therefore, the present invention has fully utilized each component of mixed c 4 alkane, obtains the higher MTBE of added value and/or iso-butylene, greatly improves the added value of mixed c 4 alkane.
Accompanying drawing explanation
Fig. 1 is the process flow diagram used in the embodiment of the present invention 1 ~ 3,
Fig. 2 is the process flow diagram of comparative example 1;
And as follows to the description of reference numerals in Fig. 1 and Fig. 2,
In Fig. 1: A, first paragraph hydrogenation unit; B, second segment hydrogenation unit; C, dehydrogenation unit; D, isomerization unit; E, etherificate unit; F, cracking unit.1, mixed c 4 alkane; 2, the material after first paragraph hydrogenation; 3, the material after second segment hydrogenation; 4, the material after dehydrogenation; 5, the material after isomerization; 6, MTBE; 7, the leftover materials after etherificate.
In Fig. 2: G, etherificate unit; H, the first rectification cell; I, selective hydrogenation unit; J, the second rectification cell.8, the mixed c 4 after extracting removing divinyl; 9, the leftover materials after etherificate; 10, to circulate light carbon four (Trimethylmethane+n-butene); 11, light carbon four (Trimethylmethane+n-butene); 12, circulation n-butene; 13, n-butene; 14, heavy carbon four (normal butane+butene-2); 15, heavy carbon four (normal butane+butene-2).
Embodiment
Below by embodiment, the invention will be further elaborated.
Technical process is as shown in Figure 1 used to prepare iso-butylene in following embodiment 1 ~ 3.From steam cracking device, catalytic cracking unit or carbon four the mixed c 4 of deep processing device through one or more pre-treatment step, the residue logistics after being proposed by the olefin fraction being easy to extract wherein is corresponding mixed c 4 alkane.Described mixed c 4 alkane 1 is introduced into first paragraph hydrogenation unit A, by full hydrogenation, unsaturated hydrocarbons is converted into alkane, material 2 after first paragraph hydrogenation enters second segment hydrogenation unit B, the removing impurity such as sulphur, nitrogen wherein, material 3 after hydrogenation removal of impurities enters dehydrogenation unit C, generate n-butene and iso-butylene, the material 4 after dehydrogenation enters isomerization unit D, and n-butene is isomerized to iso-butylene; Material after isomerization 5 is by etherificate unit E, and iso-butylene wherein and methyl alcohol react to be produced gasoline dope MTBE product 6, MTBE product 6 and be further converted to highly purified iso-butylene by cracking unit F.Leftover materials after etherificate 7 capable of circulation times hydrogenation unit A and/or hydrogenation unit B to continue for preparing iso-butylene, or provide heat for hydrogenator, dehydrogenation reactor and isomerizing reactor, or as the raw material of steam cracking device.
Embodiment 1
Shown in Fig. 1, come from consisting of of the mixed c 4 alkane of steam cracking device: Trimethylmethane: 45wt%, normal butane: 43wt%, divinyl: 2wt%, iso-butylene: 3wt%, butene-1: 4wt%, butene-2: 3wt%.One-stage hydrogenation catalyzer is alumina load metallic nickel, and object is that the hydrogenation of olefins in material is converted into alkane, and hydrogenation of olefins transformation efficiency can reach 99%.Secondary hydrogenation catalyzer is the cobalt metal of alumina load, molybdenum and nickel, and object is removed by the sulphur in material, and sulphur content can be down to below 5ppm by this catalyzer.Butane dehydrogenation adopts fluidized-bed reactor, and catalyzer is alumina load metal platinum and tin, and butane dehydrogenation is generated n-butene and iso-butylene, normal butane conversion rate of dehydrogenation is about 30%, n-butene selectivity is about 90%, and dehydrogenation of isobutane transformation efficiency is about 50%, and selectivity is about 92%.N-butene isomery turns to iso-butylene and adopts single hop fixed-bed reactor, and catalyzer is ZSM-5 molecular sieve, and n-butene conversion is about 43%, and selectivity is about 82%.Ether-based device adopts catalytic distillation reactor, and catalyzer is macropore strong acid cation exchange resin, and isobutene conversion about 95%, MTBE selectivity is about 98%.MTBE cracker adopts fixed-bed reactor, and catalyzer is the acid catalysts of alumina load, and MTBE transformation efficiency is about 91%, and selectivity is about 97%.
Embodiment 2
Shown in Fig. 1, come from consisting of of the mixed c 4 alkane of catalytic cracking unit: Trimethylmethane: 30wt%, normal butane: 50wt%, divinyl: 4wt%, iso-butylene: 6wt%, butene-1: 7wt%, butene-2: 3wt%.One-stage hydrogenation catalyzer is alumina load palladium metal, and hydrogenation of olefins transformation efficiency is about 99%.Secondary hydrogenation catalyzer is the cobalt metal of alumina load, molybdenum and nickel, and after hydrogenation, sulphur content is down to below 5ppm.Butane dehydrogenation adopts fixed-bed reactor, and catalyzer is alumina load metal platinum, tin, potassium and magnesium, and normal butane conversion rate of dehydrogenation is about 28%, and n-butene selectivity is about 91%, and dehydrogenation of isobutane transformation efficiency is about 52%, and selectivity is about 91%.N-butene isomery turns to iso-butylene and adopts single hop fixed-bed reactor, and catalyzer is ZSM-5 molecular sieve, and n-butene conversion is about 47%, and selectivity is about 84%.Ether-based device adopts catalytic distillation reactor, and catalyzer is macropore strong acid cation exchange resin, and isobutene conversion about 95%, MTBE selectivity is about 98%.MTBE cracker adopts fixed-bed reactor, and catalyzer is the acid catalysts of alumina load, and MTBE transformation efficiency is about 91%, and selectivity is about 97%.
Embodiment 3
Shown in Fig. 1, come from consisting of of the mixed c 4 alkane of carbon four deep processing device: Trimethylmethane: 34wt%, normal butane: 50wt%, divinyl: 1wt%, iso-butylene: 10wt%, butene-1: 3wt%, butene-2: 2wt%.One-stage hydrogenation catalyzer is alumina load palladium metal, and hydrogenation of olefins transformation efficiency is about 99%.Secondary hydrogenation catalyzer is the cobalt metal of alumina load, molybdenum and nickel, and after hydrogenation, sulphur content is down to below 5ppm.Butane dehydrogenation adopts fixed-bed reactor, and catalyzer is alumina load metal platinum, tin, potassium, magnesium and zinc, and normal butane conversion rate of dehydrogenation is about 31%, and n-butene selectivity is about 89%, and dehydrogenation of isobutane transformation efficiency is about 51%, and selectivity is about 91%.N-butene isomery turns to iso-butylene and adopts single hop fixed-bed reactor, and catalyzer is the SAPO zeolite molecular sieve of magnesium alkali metals modified, and n-butene conversion is about 48%, and selectivity is about 83%.Ether-based device adopts catalytic distillation reactor, and catalyzer is macropore strong acid cation exchange resin, and isobutene conversion about 95%, MTBE selectivity is about 98%.MTBE cracker adopts fixed-bed reactor, and catalyzer is the acid catalysts of alumina load, and MTBE transformation efficiency is about 91%, and selectivity is about 97%.
Comparative example 1
According to the scheme implementation described in document DE102008007081, namely as shown in Figure 2, consisting of of the mixed c 48 after extracting removing divinyl: Trimethylmethane: 5wt%, normal butane: 11wt%, iso-butylene: 45wt%, butene-1: 21wt%, butene-2: 18wt%.Adopt the method, the yield of iso-butylene is about 48%, and the rate of recovery of butene-1 is about 66%, and all the other are still unemployed mixed c 4.
Claims (8)
1. prepare a method of MTBE with mixed c 4 alkane, comprise the following steps,
Steps A, first paragraph hydrogenation: to remove the unsaturated hydrocarbons in described mixed c 4 alkane;
Step B, second segment hydrogenation: with the sulfur impurity in removing step A product and/or nitrogen;
Step C, dehydrogenation: the product dehydrogenation of step B is converted into n-butene and iso-butylene;
Step D, isomerization: the product of step C is passed into isomerization unit, makes n-butene wherein tautomerize to iso-butylene;
Step e, etherificate: the product of step D is passed into ether-based device, iso-butylene wherein and methyl alcohol react and generate described MTBE.
2. method according to claim 1, is characterized in that, the butane content in described mixed c 4 alkane is more than 50wt%, preferred more than 65wt%, more preferably more than 80wt%.
3. method according to claim 1 and 2, is characterized in that, to be returned by the leftover materials after the etherificate comprising butane and C 4 olefin in steps A and/or step B and to make it as the raw material of the described MTBE of preparation.
4. method according to claim 1 and 2, is characterized in that, provides heat by the leftover materials burning after the etherificate comprising butane and C 4 olefin thus for any one or more reactors in steps A ~ D.
5. method according to claim 1 and 2, is characterized in that, using the raw material of the leftover materials after the etherificate comprising butane and C 4 olefin as steam cracking device.
6. according to the method in Claims 1 to 5 described in any one, it is characterized in that, described mixed c 4 alkane comes from crude refining device, steam cracking device, catalytic cracking unit and/or carbon four mixed c 4 by product of deep processing device.
7. according to the method in Claims 1 to 5 described in any one, it is characterized in that, the catalyzer used in steps A is alumina load metallic nickel, zinc and/or palladium, the catalyzer used in step B is alumina load metal molybdenum, cobalt and/or nickel, the catalyzer used in step C is alumina load metal platinum, tin and/or zinc, the catalyzer used in step D is the SAPO being selected from modification, one or more in ZSM and zeolite molecular sieve, the catalyzer used in step e is for being selected from macropore strong acid cation exchange resin, one or more in ZSM-5 molecular sieve and heteropolyacid.
8. prepare a method for iso-butylene with mixed c 4 alkane, it is characterized in that, first prepare MTBE with method described in any one in as above claim 1 ~ 7, more described MTBE cracking is obtained described iso-butylene.
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| CN106867578A (en) * | 2015-12-14 | 2017-06-20 | 中国石油天然气股份有限公司 | A kind of trans-utilization technique of lower carbon number hydrocarbons |
| CN106867563A (en) * | 2015-12-14 | 2017-06-20 | 中国石油天然气股份有限公司 | A kind of method for converting plug oils lighter hydrocarbons |
| CN108117482A (en) * | 2017-12-12 | 2018-06-05 | 北京石油化工工程有限公司 | A kind of refinery's by-product C_4 hydrocarbon and liquefied gas comprehensive processing and utilization device and method |
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| CN112441866A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Method for producing n-butene from isobutene |
| CN114456030A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Comprehensive utilization method of mixed carbon four-carbon five-material |
| CN115073254A (en) * | 2022-06-15 | 2022-09-20 | 宁波昊德化学工业股份有限公司 | Production method and production equipment of isobutene |
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| CN106867563B (en) * | 2015-12-14 | 2018-10-16 | 中国石油天然气股份有限公司 | A method of conversion plug oils lighter hydrocarbons |
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| CN110437873A (en) * | 2018-05-03 | 2019-11-12 | 中国石油天然气股份有限公司 | A kind of utilization method of the hydrocarbon ils rich in four C 5 alkane of carbon |
| CN110437873B (en) * | 2018-05-03 | 2021-09-28 | 中国石油天然气股份有限公司 | Utilization method of hydrocarbon oil rich in carbon four-carbon pentaalkane |
| CN112441866A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Method for producing n-butene from isobutene |
| CN112441866B (en) * | 2019-09-04 | 2022-08-09 | 中国石油化工股份有限公司 | Method for producing n-butene from isobutene |
| CN114456030A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Comprehensive utilization method of mixed carbon four-carbon five-material |
| CN114456030B (en) * | 2020-10-22 | 2024-05-07 | 中国石油化工股份有限公司 | Comprehensive utilization method of mixed C-four-C-five materials |
| CN115073254A (en) * | 2022-06-15 | 2022-09-20 | 宁波昊德化学工业股份有限公司 | Production method and production equipment of isobutene |
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