CN102267853A - Method for producing 1-butene through 2-butene isomerization - Google Patents
Method for producing 1-butene through 2-butene isomerization Download PDFInfo
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- CN102267853A CN102267853A CN201110256673XA CN201110256673A CN102267853A CN 102267853 A CN102267853 A CN 102267853A CN 201110256673X A CN201110256673X A CN 201110256673XA CN 201110256673 A CN201110256673 A CN 201110256673A CN 102267853 A CN102267853 A CN 102267853A
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Abstract
The invention discloses a method for producing 1-butene through 2-butene isomerization, and the method is characterized by comprising the following steps of: baking alumina used as a catalyst carrier at the temperature of 400-600 DEG C for 1-12 hours to control the surface area of the alumina at 150-210 m<2>/g; then dissolving 0.146-23.82 parts by weight of a metal salt in 82-100 parts by weight of deionized water to prepare an aqueous solution, then feeding 57 parts by weight of the baked catalyst carrier into the metal salt solution, and standing and immersing at room temperature for 16-24 hours; filtering out residual liquid, baking at the temperature of 120-160 DEG C for 4-10 hours to completely remove water, and then baking at the temperature of 500-600 DEG C for 1-12 hours to prepare a metal composite oxide catalyst; and loading the prepared catalyst in a fixed bed catalytic reactor, passing 2-butene gas with the purity of 85.0-99.0% through a catalyst bed layer, carrying out double-bond isomerization at the temperature of 300-480 DEG C, pressure of 0.1-0.5 MPa and feeding gas space velocity of 2-butene being 60-900/h, and sampling and analyzing the reacted gas timely to prepare 1-butene with the purity of 19.0-27.0%.
Description
Technical field
The present invention relates to a kind of 2-butylene isomerization and produce the method for 1-butylene, belong to the organic catalysis field.
Background technology
C
41-butylene in the alkene is a kind of alpha-olefin, and chemical property is active, and is of many uses.The main application of 1-butylene is the comonomer of preparation linear low density polyethylene (LLDPE).1-butylene generates the mixing valeral based on valeraldehyde by hydroformylation reaction, and valeral is the main raw material of synthetic senior softening agent through the isodecyl alcohol of condensation and hydrogenation reaction generation.Because 1-butylene is of many uses, demand in recent years sharply increases.
The source of 1-butylene mainly contains:
1. the byproduct that obtains when carrying out catalytic cracking or thermally splitting in the oil refining production process;
2. the byproduct that obtains when producing other alkene when stable hydrocarbon carries out steam cracking;
3. ethene obtains 1-butylene by oligomerisation reaction;
4.C
4Hydrocarbon mixture obtains 1-butylene through separating extracting.
C
4The reactive behavior of 2-butylene is poor in the alkene, and the using value in chemical industry is very low, and main purposes is to use as geseous fuel at present.But by the method for catalyzed conversion, the position of double bond isomerization reaction can take place and generate 1-butylene in 2-butylene under suitable condition.But when the isomerization of 2-butylene position of double bond, possible generating portion carbon chain isomer product iso-butylene and a small amount of carbon number are less than 4 split product.So 2-butylene can be used for industrial production by the process of position of double bond isomerization generation 1-butylene, gordian technique is that well behaved catalyzer will be arranged.This catalyzer should have high reactivity, also can suppress carbon chain isomerization and scission reaction to greatest extent, also requires good stability simultaneously, and life cycle is long.
" research of 2-butylene isomerization catalyst " (petrochemical complex, 18 (2), 1989,75~80) have been introduced at Al
2O
3Transition metal oxides such as last load Mn, Co, Cr and Fe carry out modification, are used for the reaction that the 2-butylene isomery turns to 1-butylene.Wherein the catalyzer after the load 0.4% Mn oxide modification not only has high reaction activity and high, and can suppress the generation of iso-butylene effectively, and split product also seldom simultaneously.But do not report the stability of catalyzer in this article.
U.S. Pat P4814542 has introduced with γ-Al
2O
3Be main component, wherein contain SiO
2And the catalyzer of a kind of or several metal oxide compound in IIA family, VIII family or the lanthanon in the periodic table of elements.Catalyzer is to thermally-stabilised, and iso-butylene content is low when 2-butylene changes into 1-butylene, and the 1-butylene after separating can reach the level of polymerization-grade.But this patent is not reported the work-ing life of catalyzer.
Introduced among the Chinese patent CN101121623A and a kind ofly changed into the method for 1-butylene by 2-butylene by catalysis process, used catalyzer is pure silicon molecular sieve, silica alumina ratio SiO
2/ Al
2O
3Be 5~1000 crystal aluminosilicate and ZSM-5, ZSM-35, ZSM-11 or the ZSM-42 in the ZSM molecular sieve, its silica alumina ratio SiO
2/ Al
2O
3Between 50~600, catalyzer is checked and rated through 1700h, and 2-butylene transformation efficiency and product yield remain unchanged substantially.But do not see the introduction of side reaction situation.The molecular sieve price is more expensive, and being used for industrial production cost height is its shortcoming.
In the isomerization reaction of 2-butylene position of double bond, the fracture that often is attended by C-C generates split product, the carbochain skeletal isomerization also may take place generate iso-butylene.Though it is more catalysis 2-butylene position of double bond to be isomerizated into the catalyzer of 1-butylene, as metal oxide, metal sulfate and phosphoric acid salt, loaded noble metal catalyst, molecular sieve, ionic liquid etc., but catalytic activity is good, selectivity is high and good stability, and the catalyzer with industrial application value is actually rare.
Summary of the invention
The present invention seeks to provides a kind of 2-butylene isomerization to produce the method for 1-butylene at the deficiencies in the prior art, be characterized in guaranteeing that catalyzer has the highly active while, improve the selectivity and the thermostability of isomerization catalyst, reduce the cost of catalyzer, make it in commercial process, to obtain broader applications, produce good economic benefit and environmental benefit.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The method that 1-butylene is produced in the 2-butylene isomerization may further comprise the steps:
(1). Preparation of catalysts
With catalyst carrier alumina, at 400~600 ℃ of roasting 1~12h of temperature, the aluminum oxide specific surface area is at 150~210m
2/ g; Metal-salt 0.146~23.82 weight part is dissolved in 82~100 parts by weight of deionized water is mixed with the aqueous solution, then support of the catalyst 57 weight parts that roasting is good are dropped in the above-mentioned metal salt solution, under room temperature, flood 16~24h, the liquid that elimination is residual, remove fully to moisture at 120~160 ℃ of temperature baking, 4~10h, at 500~600 ℃ of roasting 1~12h of temperature, make the different metal composite oxide catalysts again;
(2) the .2-isomerization of butene is produced 1-butylene
Catalyzer with method for preparing, fill in the fixed bed catalytic reactor, allow content at 85.0~99.0% 2-butylene gas by beds, in 300~480 ℃ of temperature, pressure 0.1~0.5MPa, the gas hourly space velocity of the charging of 2-butylene are 60~600h
-1Condition under, carry out double bond isomerization reaction, reacted gas timing sampling is analyzed, making 1-butylene content is 19.0~27.0%.
Metal-salt is at least a in yellow soda ash, Repone K, single nickel salt and the Palladous chloride.
Contain at least a oxide compound in sodium, potassium, nickel and the palladium in the catalyzer, charge capacity is 0.15~10% of an alumina catalyst support weight.
The weight of each component is respectively aluminum oxide 95.0~99.85% in the catalyzer, sodium oxide 0.15~5.0%.
The weight of each component is respectively aluminum oxide 95.0~99.75% in the catalyzer, sodium oxide 0.15~1.0%, potassium oxide 0.1~4.0%.
The weight of each component is respectively aluminum oxide 93.0~99.75% in the catalyzer, sodium oxide 0.15~2.0%, palladous oxide 0.1~5.0%.
The weight of each component is respectively aluminum oxide 87.0~99.35% in the catalyzer, sodium oxide 0.15~3.0%, nickel oxide 0.5~10%.
Performance test:
The specific surface area of catalyzer adopts the BET method.
The content assaying method of each metal oxide is in the catalyzer: will make solution after the catalyst dissolution, measure each metal component metal content with the ICP method, be converted to metal oxide content again.
The catalyst performance test adopts fixed bed catalytic reactor to estimate its activity, selectivity and stability.
Each composition of raw material and reaction product adopts gc analysis.
The present invention has following advantage:
1. innovation part of the present invention is, having developed a class is carrier with the aluminum oxide, the composite oxide catalysts that contains one or more metal oxides, be used for 2-butylene generates 1-butylene by the position of double bond isomerization reaction, this based composite oxide catalyzer has high activity and selectivity, under lower reaction pressure, each components contents can reach or forms near thermodynamic(al)equilibrium under the temperature of reaction in the product.Under 450 ℃ of temperature or higher temperature, the iso-butylene that 1-butylene split product and skeletal isomerization generate still seldom or do not detect, this class catalyzer price is more cheap, is easy to suitability for industrialized production.
2. change into by the position of double bond isomerization in the process of 1-butylene at 2-butylene, the L acid of catalyst surface is catalytic active center.Aluminum oxide becomes γ-Al through roasting under proper temperature
2O
3After, the surface has the L acid site.But the γ-Al of the different trades mark
2O
3The surface the L acid site differ bigger, if be directly used in isomerization reaction, often there will be two kinds of situations: as surface acidity too a little less than, catalytic activity is low; Too strong as surface acidity, though catalytic activity is very high, selectivity is very poor, generates a large amount of iso-butylenes and split product, and both summations can be up to about 25%, and the easy carbon distribution of catalyst surface make active descend very fast.In alumina supporter, add metal oxide, the performance of catalyzer is carried out modification, acid-basicity that can the regulating catalyst surface, thus improve catalytic performance.The kind of the metal oxide that is added and the content in catalyzer have decisive influence to the modulation degree of the acid-basicity of catalyst surface, and this will directly have influence on the stability of activity, selectivity and the catalyzer of isomerization reaction.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1~6
According to Na
2The ratio of O charge capacity 0.35% prepares loaded catalyst, with 0.340 gram anhydrous sodium carbonate, is dissolved in the 82ml deionized water, is taken at 500 ℃ of baked strip Al of temperature again
2O
3Carrier 100ml, size is Ф 3 * 8~10mm, weight 57 grams are with Al
2O
3Carrier is put in the sodium carbonate solution, dipping 16h, and the liquid that elimination is residual, standby after 500 ℃ of roastings of temperature in 120 ℃ of oven dry of temperature, Na in the catalyzer
2O content is 0.35%, and the specific surface area of catalyzer is 205m
2/ g.
Above-mentioned loaded catalyst is packed in the fixed bed catalytic reactor, feed 2-butylene gas, this gas main component is: anti--2-butylene 64.3%, suitable-2-butylene 33.0%, and 1-butylene 2.7%, reaction conditions is: pressure 0.1MPa, gas hourly space velocity 240h
-1, the content of 1-butylene, iso-butylene and split product is detailed in the reaction product under the differing temps is shown in Table 1:
Embodiment 7~10
According to K
2O charge capacity 0.60% and Na
2The ratio of O charge capacity 0.15% prepares loaded catalyst, and with 0.546 gram Repone K, 0.147 gram anhydrous sodium carbonate is dissolved in the 85ml deionized water, is taken at 600 ℃ of baked strip Al of temperature
2O
3Carrier 100ml, size is Ф 3 * 8~10mm, weight 57 grams are with Al
2O
3Carrier is put in the mixing solutions of Repone K and yellow soda ash, flooded 24 hours, and the liquid that elimination is residual, standby after 500 ℃ of roastings of temperature in 120 ℃ of oven dry of temperature, K in the catalyzer
2O content is 0.60%, Na
2O content is 0.15%, and the specific surface area of catalyzer is 180m
2/ g.
Above-mentioned loaded catalyst is packed in the fixed bed catalytic reactor, feed 2-butylene gas.This gas main component is: anti--2-butylene 64.3%, suitable-2-butylene 33.0%, and 1-butylene 2.7%.Reaction conditions is: 450 ℃ of temperature, and pressure 0.5MPa, under the different gas hourly space velocities, 1-butylene, iso-butylene and split product content are detailed in the reaction product is shown in Table 2.
Embodiment 11
According to Na
2The ratio of O charge capacity 2.0% prepares loaded catalyst, with 1.99 gram anhydrous sodium carbonates, is dissolved in the 95ml deionized water, is taken at 550 ℃ of baked strip Al of temperature again
2O
3Carrier 100ml, size is Ф 3 * 8~10mm, weight 57 grams are with Al
2O
3Carrier is put in the sodium carbonate solution, dipping 18h, and the liquid that elimination is residual, standby after 600 ℃ of roastings of temperature in 120 ℃ of oven dry of temperature, Na in the catalyzer
2O content is 2.0%, and the specific surface area of catalyzer is 150m
2/ g.
Above-mentioned loaded catalyst is packed in the fixed bed catalytic reactor, feed 2-butylene gas, this gas main component is: anti--2-butylene 64.3%, suitable-2-butylene 33.0%, 1-butylene 2.7%, reaction conditions is: 450 ℃ of temperature, pressure 0.1MPa, gas hourly space velocity 60h
-1, 1-butylene content is 23.1% in the reaction product, iso-butylene content 0.0%.
Embodiment 12
According to the method for embodiment 7, preparation K
2O content is 0.60%, Na
2O content is 0.15% catalyzer.Above-mentioned loaded catalyst is packed in the fixed bed catalytic reactor, feed 2-butylene gas, this gas main component is: anti--2-butylene 64.3%, suitable-2-butylene 33.0%, and 1-butylene 2.7%.Reaction conditions is: 480 ℃ of temperature, pressure 0.1MPa, gas hourly space velocity 300h
-1, 1-butylene content is 27.7% in the reaction product, iso-butylene content 0.3%.
Embodiment 13
According to NiO charge capacity 0.63% and Na
2The ratio of O charge capacity 0.15% prepares loaded catalyst.1.367 gram seven water single nickel salts and 0.148 gram anhydrous sodium carbonate are dissolved in the 100ml deionized water, are taken at 550 ℃ of baked strip Al of temperature again
2O
3Carrier 100ml, size is Ф 3 * 8~10mm, weight 57 grams are with Al
2O
3Carrier is put in single nickel salt and the sodium carbonate mixture, flooded 20 hours, and elimination metal remained salt liquid, in 120 ℃ of oven dry of temperature, standby after 550 ℃ of roastings of temperature, NiO content is 0.63% in the catalyzer, Na
2O content is 0.15%, and the specific surface area of catalyzer is 160m
2/ g.
Above-mentioned loaded catalyst to be packed in the fixed bed catalytic reactor, feed 2-butylene gas, this gas main component be instead-2-butylene: 64.3%, suitable-2-butylene: 33.0%, 1-butylene 2.7%.Reaction conditions is: 320 ℃ of temperature, pressure 0.2MPa, gas hourly space velocity 300h
-1, 1-butylene content is 21.0% in the reaction product, iso-butylene content 0.7%.
Embodiment 14
According to PdO charge capacity 0.23% and Na
2The ratio of O charge capacity 0.15% prepares loaded catalyst, and 0.190 gram Palladous chloride is dissolved in the 49ml deionized water, adds the 1ml concentrated hydrochloric acid again, and low-grade fever to Palladous chloride dissolves fully; Again with 0.147 the gram anhydrous sodium carbonate be dissolved in the 50ml deionized water, two kinds of solution are mixed, treat bubble collapse after, be taken at 500 ℃ of baked strip Al of temperature
2O
3Carrier 100ml, size is Ф 3 * 8~10mm, weight 57 grams are with Al
2O
3Carrier is put in Palladous chloride and the sodium carbonate mixture, flooded 16 hours, and the liquid that elimination is residual, in 120 ℃ of oven dry of temperature, standby after 500 ℃ of roastings of temperature, PdO content is 0.23% in the catalyzer, Na
2O content is 0.15%, and the specific surface area of catalyzer is 180m
2/ g.
Above-mentioned loaded catalyst is packed in the fixed bed catalytic reactor, feed 2-butylene gas, this gas main component is: anti--2-butylene 64.3%, suitable-2-butylene 33.0%, and 1-butylene 2.7%.Reaction conditions is: 350 ℃ of temperature, pressure 0.3MPa, gas hourly space velocity 180h
-1, 1-butylene content is 21.2% in the reaction product, iso-butylene content 0.7%.
Embodiment 15
According to the method for embodiment 1, preparation Na
2The catalyzer of O charge capacity 0.80%.Above-mentioned loaded catalyst is packed in the fixed bed catalytic reactor, feed 2-butylene gas, this gas main component is: anti--2-butylene 64.3%, suitable-2-butylene 33.0%, and 1-butylene 2.7%.350 ℃ of temperature, pressure 0.1MPa, gas hourly space velocity is at 200~300h
-1In the scope, the experiment through 500 hours, in the reaction product 1-butylene stable content 21.5~22.0%, iso-butylene content 0.2%, do not detect split product, the good stability of catalyzer is described.
Table 1
Sequence number | Temperature of reaction (℃) | 1-butylene (%) | Iso-butylene (%) | Split product (%) |
1 | 300 | 19.2 | 0.1 | Detection less than |
2 | 320 | 19.8 | 0.1 | Detection less than |
3 | 350 | 20.9 | 0.2 | Detection less than |
4 | 400 | 24.0 | 0.5 | Detection less than |
5 | 420 | 25.0 | 0.7 | Detection less than |
6 | 450 | 27.2 | 0.9 | Detection less than |
Table 2
Sequence number | Gas hourly space velocity (h -1) | 1-butylene (%) | Iso-butylene (%) | Split product (%) |
7 | ?180 | 26.9 | 0.2 | Detection less than |
8 | ?300 | 26.8 | 0.2 | Detection less than |
9 | ?480 | 26.3 | 0.1 | Detection less than |
10 | ?600 | 26.3 | 0.1 | Detection less than |
Claims (7)
1. the method for 1-butylene is produced in a 2-butylene isomerization, it is characterized in that this method may further comprise the steps:
(1). Preparation of catalysts
With catalyst carrier alumina, at 400~600 ℃ of roasting 1~12h of temperature, the aluminum oxide specific surface area is at 150~210m
2/ g; Metal-salt 0.146~23.82 weight part is dissolved in 82~100 parts by weight of deionized water is mixed with the aqueous solution, then support of the catalyst 57 weight parts that roasting is good are dropped in the above-mentioned metal salt solution, under room temperature, leave standstill dipping 16~24h, the liquid that elimination is residual, remove fully to moisture at 120~160 ℃ of temperature baking, 4~10h, at 500~600 ℃ of roasting 1~12h of temperature, make metal composite oxide catalyst again;
(2) the .2-isomerization of butene is produced 1-butylene
Catalyzer with method for preparing, fill in the fixed bed catalytic reactor, allow content at 85.0~99.0% 2-butylene gas by beds, in 300~480 ℃ of temperature, pressure 0.1~0.5MPa, the gas hourly space velocity of the charging of 2-butylene are 60~900h
-1Condition under, carry out double bond isomerization reaction, reacted gas timing sampling is analyzed, making 1-butylene content is 19.0~27.0%.
2. the 2-butylene isomerization method of producing 1-butylene according to claim 1 is characterized in that metal-salt is at least a in yellow soda ash, Repone K, single nickel salt and the Palladous chloride.
3. the 2-butylene isomerization method of producing 1-butylene according to claim 1 is characterized in that containing in the catalyzer at least a oxide compound in sodium, potassium, nickel or the palladium, and charge capacity is 0.15~10% of a catalyst weight.
4. produce the method for 1-butylene as 2-butylene isomerization as described in the claim 3,, it is characterized in that the weight of each component is respectively aluminum oxide 95.0~99.85% in the catalyzer, sodium oxide 0.15~5.0%.
5. produce the method for 1-butylene as 2-butylene isomerization as described in the claim 3, it is characterized in that the weight of each component is respectively aluminum oxide 95.0~99.75% in the catalyzer, sodium oxide 0.15~1.0%, potassium oxide 0.1~4.0%.
6. produce the method for 1-butylene as 2-butylene isomerization as described in the claim 3, it is characterized in that the weight of each component is respectively aluminum oxide 93.0~99.75% in the catalyzer, sodium oxide 0.15~2.0%, palladous oxide 0.1~5.0%.
7. the method for producing 1-butylene as 2-butylene isomerization as described in the claim 3 is characterized in that the weight of each component is respectively aluminum oxide 87.0~99.35% in the catalyzer, sodium oxide 0.15~3.0%, nickel oxide 0.5~10%.
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CN106552621A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | 2-butylene hydro-isomerization prepares the catalyst used by 1-butylene and prepares the method for 1-butylene |
CN108283924A (en) * | 2017-10-23 | 2018-07-17 | 王卓 | A kind of preparation method of olefines double bond isomerizing catalyst |
CN110201713A (en) * | 2019-06-17 | 2019-09-06 | 万华化学集团股份有限公司 | A kind of catalyst and preparation method thereof and the application in olefin isomerization reaction |
CN113122313A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Olefin isomerization method |
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Cited By (6)
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CN106552621A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | 2-butylene hydro-isomerization prepares the catalyst used by 1-butylene and prepares the method for 1-butylene |
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CN110201713A (en) * | 2019-06-17 | 2019-09-06 | 万华化学集团股份有限公司 | A kind of catalyst and preparation method thereof and the application in olefin isomerization reaction |
CN110201713B (en) * | 2019-06-17 | 2022-03-11 | 万华化学集团股份有限公司 | Catalyst, preparation method thereof and application thereof in olefin isomerization reaction |
CN113122313A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Olefin isomerization method |
CN113122313B (en) * | 2020-01-15 | 2023-06-30 | 中国石油天然气股份有限公司 | Olefin isomerization method |
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Application publication date: 20111207 |