CN101225020B - Method for preparing isobutanol by using mixed C4 or isobutene as raw materials - Google Patents
Method for preparing isobutanol by using mixed C4 or isobutene as raw materials Download PDFInfo
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- CN101225020B CN101225020B CN2008100335885A CN200810033588A CN101225020B CN 101225020 B CN101225020 B CN 101225020B CN 2008100335885 A CN2008100335885 A CN 2008100335885A CN 200810033588 A CN200810033588 A CN 200810033588A CN 101225020 B CN101225020 B CN 101225020B
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Abstract
The invention provides a preparation method for isobutanol with mixed C4, raffinate C4 or isobutane as the material; wherein, the refinery mixed C4 is obtained from the by-product in the process of refining and producing fuel oil with crude oil; and the raffinate mixed C4 is obtained from the by-product after extraction of butadiene in the process of producing ethylene and propylene with the steam cracking method. The preparation method for isobutanol is characterized in that the isobutanol is prepared via three steps of reactions as follows: (1) isobutene or tert-butyl alcohol is separated and prepared from the refinery mixed C4 or the steam-cracking raffinate C4, or isobutene is prepared via catalytic dehydrogenation of the isobutane; (2) methacrolein is prepared via selective oxidationof the isobutene or the tert-butyl alcohol under the action of the catalyst of molybdenum-bismuth composite oxide; (3) the isobutanol is prepared via hydrogenation of the methacrolein under the action of the nickel catalyst. The preparation method for isobutanol with mixed C4, raffinate C4 or isobutane as the material has the advantages that the material has a low price and is easy to obtain; dependence of the high-priced propylene as the material of C3 in the original production of isobutanol is broken; a new technique route using C4 with low utilization ratio to prepare isobutanol is created; technique is simple; yield of isobutanol is high; production cost is low; and scale production is easy.
Description
Technical field
The present invention relates to a kind of refinery's mixed C of producing the catalytic cracking unit by-product of oil fuel with crude refining
4, steam cracking device produce ethene and propylene by-product and the extracting divinyl after take out surplus mixed C
4Or Trimethylmethane is the method for feedstock production isopropylcarbinol.
Technical background
Isopropylcarbinol is a kind of important basic chemical industry raw material, can be used for making petroleum additive, antioxidant, softening agent, synthetic rubber, synthetic musk, fruit essential oil and synthetic drugs etc.Its ester derivative such as isobutyl acetate, isobutyl butyrate, isobutyl lactate etc. can be used as solvent and use in coating industry; In addition, sebacic acid isobutyl ester and longer chain fatty acid isobutyl ester can be used to synthetic lubricant and hydraulic efficiency oil.Isopropylcarbinol also is widely used as the thinner of celluloid lacquer, increasing its gloss and flowability, and prevents that it from fading.
At present, isopropylcarbinol mainly comes from the isobutyric aldehyde hydrogenation of propylene carbonylation production fourth/octanol device by-product, but along with of the development of propylene oxo process to low-pressure process (rhodium catalyst method), make the positive isomery ratio in the thick oxo process liquid rise to about 10: 1, reduce day by day in the source of hydrogenating materials isobutyric aldehyde, and this route is from propylene preparation isopropylcarbinol in short supply in the world, along with the hurricane of International Crude Oil rises, also when the river rises the boat goes up for the propylene price, the corresponding raw materials cost that increased; On the other hand, in this route product multiple isomers is arranged, as butyraldehyde-n and isobutyric aldehyde or propyl carbinol and isopropylcarbinol, the product separating difficulty is bigger.Therefore, at present in the world all at the new route of synthesis of exploring isopropylcarbinol.
The synthetic gas of producing through gas making with Sweet natural gas or coal is the feedstock production isopropylcarbinol, is a kind of novel method of the more preparation isopropylcarbinol of research both at home and abroad at present.Though the synthetic isopropylcarbinol of this route has been obtained certain progress at present, as the Pd/ZrO that modifies with basic metal or alkaline earth metal oxide among the EP0208102
2Catalyzer carries out the reaction of synthetic gas system isopropylcarbinol, and the isopropylcarbinol yield reaches 38.3%; The Mg-Zn-Zr that modifies with alkali metal promoter among the US5811602 is that catalyzer carries out the reaction of synthetic gas system isopropylcarbinol, and the highest yield of isopropylcarbinol reaches 40.1% in the product, but product component is very complicated, and the isopropylcarbinol selectivity is lower.Except that isopropylcarbinol, also contain methyl alcohol in the product, ethanol, n-propyl alcohol, propyl carbinol, Virahol, the trimethyl carbinol, sec-butyl alcohol, multiple alcohols such as Pentyl alcohol, these alcohol belong to homologue or isomers, obtain the higher commodity isopropylcarbinol of purity or other alcohols materials, must carry out loaded down with trivial details aftertreatment to product, the corresponding production cost that increased, and it is relatively poor to separate the isopropylcarbinol purity that obtains, as patent US5756866 product has been carried out refining separation, but the isopropylcarbinol purity that obtains can only reach 95%, does not reach the purity requirement of industrial salable product isopropylcarbinol 99.0% as yet.Thereby the mixture of lower alcohols that is made by synthetic gas is general and purify without separating, and the use that only acts as a fuel.
The C of catalytic cracking unit or steam cracking device by-product
4Purposes is less, and relative low price if can be with C
4For raw material obtains isopropylcarbinol, on the one hand will reduce the production cost of isopropylcarbinol greatly, the isopropylcarbinol production that can break traditions on the other hand is for the dependence of propylene, undoubtedly with significant.Produce the mixed C of the catalytic cracking unit by-product of oil fuel from crude refining
4In or produce the surplus C that takes out of ethene and propylene by-product from steam cracking device
4Middle technology of separating the preparation iso-butylene or the trimethyl carbinol, perhaps Trimethylmethane (comes from mixed C
4Or oil field gas) catalytic dehydrogenation prepares the technology of iso-butylene, and is all ripe relatively at present; Iso-butylene or trimethyl carbinol selective oxidation prepare the also existing industrialized report of Methylacrylaldehyde; And the further hydrogenation preparing isopropylcarbinol of Methylacrylaldehyde also is feasible theoretically, but does not see bibliographical information both at home and abroad as yet at present.Therefore, these three processes are combined, form with aboundresources and mixed C cheap and easy to get
4Or oil field gas is that the synthetic isopropylcarbinol of starting raw material will be opened up a brand-new operational path for the preparation of isopropylcarbinol.
By C
4Cut (refinery's hybrid C 4 or steam cracking are taken out surplus C4) separation obtains the method for the iso-butylene or the synthetic trimethyl carbinol in document (chemical engineer, 2006,125 (2): provided comparatively detailed introduction 22-24).At C
4In the cut, because the boiling point of iso-butylene and n-butene differs only 0.6 ℃, relative volatility only differs 0.022, therefore adopt the general physical method to be difficult to it is separated, the method for industrial isobutylene separation commonly used has molecular sieve adsorption, sulfuric acid absorption method, isobutene oligomerisation method, direct hydration method or methanol etherification method.Molecular sieve adsorption is to utilize n-butene and the iso-butylene Technology that the difference of adsorptive power is come isobutylene separation on molecular sieve; Sulfuric acid absorption method is to utilize that the speed of n-butene and iso-butylene and sulfuric acid reaction is different to be realized separating of n-butene and iso-butylene; The isobutene oligomerisation method is with C
4In isobutene polymerisation generate C
8, C afterwards
8Cracking obtains iso-butylene again; Direct hydration method is with C
4In the iso-butylene catalytic hydration generate the trimethyl carbinol, the trimethyl carbinol obtains iso-butylene by an acidic catalyst dehydration again; The methanol etherification method is to contain the C of iso-butylene
4Cut and methyl alcohol carry out selective reaction and produce methyl tertiary butyl ether (MTBE), afterwards MTBE again cracking generate iso-butylene.Direct hydration method and methanol etherification method make in the several method iso-butylene yield and purity are higher, in patent CN1196757, CN1304917, CN1609082, US3665048, CN1040360, CN1418729 and US4447668, these two kinds of methods are reported respectively, by C
4The iso-butylene yield that sets out can reach 99%, and iso-butylene purity can reach 99.5%.In addition, the Trimethylmethane aboundresources mainly comes from oil field gas, Sweet natural gas and refinery gas and steam cracking tail gas, and only the output in the annual catalytic cracking gasoline gas of China just reaches more than 400 ten thousand tons, at oil field gas, Sweet natural gas and other C
4Also contain a large amount of Trimethylmethanes in the cut, but Trimethylmethane chemical utilization rate is lower at present, most of as the use of liquefied petroleum gas (LPG) (LPG) fuel, added value is very low.Prepare the Application Areas that iso-butylene has been expanded Trimethylmethane undoubtedly by dehydrogenation of isobutane.Industrialized at present dehydrogenation of isobutane technology has Oleflex, Star, Catofin, FDB-4, Linde technology, and used catalyst system has Pt series catalysts (US4430517, US5736478, CN1185352, CN1185994) and CrO
xSeries catalysts (Appl.Catal.A, 1996,144 (1-2): 335～341, Ind.Eng.Chem.Res., 2001,40:781～784, Chem.Eng.Process., 2002,41:337～347), the Trimethylmethane transformation efficiency is 50%～60%, and selective isobutene is 91%～95%.In addition, some VO just under development
x/ Al
2O
3Series catalysts (J.Catal., 1997,169 (1): 203～211, J.Catal., 2001,242～252), molybdate series catalyzer (Catal.Today, 2000,61:377～382, Appl.Catal.A 203 (1):, 1999,125～135), phosphate-based catalyzer (Appl.CatalA, 1998,170 (1): 23～31) also obtained catalytic effect preferably 182 (1):, the Trimethylmethane transformation efficiency can reach 65.1%, and selective isobutene is 93.2%.
Iso-butylene or Oxidation of t-Butanol prepare the also existing a large amount of patent report of Methylacrylaldehyde, catalyst system therefor Chang Duoyong molybdenum bismuth series catalysts, among patent CN1143946, CN1467032, CN1647853, CN1042200, US4250339 and the ZL200410084589.4 this reaction is studied in great detail, isobutene conversion is 95%～97%, and the Methylacrylaldehyde selectivity is 86%～91%.
By the existing a large amount of report of the method for saturated aldehyde or the corresponding saturated alcohol of unsaturated aldehyde hydrogenation preparing.For example described the method for saturated aldehyde such as butyraldehyde-n, isobutyric aldehyde, 2 methyl butyraldehyde, hexanal, aldehyde C-9, acetaldehyde, propionic aldehyde, different propionic aldehyde and unsaturated aldehyde such as propenal, crotonaldehyde, 2-ethyl hexenal, the corresponding saturated alcohol of 2-propyl group hexenoic aldehyde hydrogenation system among patent CN1255406, CN1251796, CN1695802, CN1883795, the US3491159: with Cu-Zn is catalyzer, at 110～200 ℃, 0.1～1.0MPa, H
2With the mol ratio of aldehyde is to carry out hydrogenation reaction under 10～200 the condition, unsaturated aldehyde or saturated aldehyde can be converted into corresponding saturated alcohol expeditiously, but above-mentioned patent all is to be that raw material carries out hydrogenation reaction with pure aldehyde.Saturated aldehyde in the actual industrial production or unsaturated aldehyde mostly are the product of olefin hydroformylation; obtain by propene hydroformylation reaction as butyraldehyde-n and isobutyric aldehyde; butyraldehyde-n obtains the 2-ethyl hexenal through the condensation dehydration reaction again, so often contain some impurity such as manthanoate, hydroxy aldehyde and some high boiling ester classes, ethers and acetal etc. in the aldehyde of actual industrial production.These impurity need carry out hydrogenation reaction equally, because also can obtain the purpose product alcohol as manthanoate and acetals impurity by hydrogenation reaction, thereby increase pure yield, and improve the economy of reaction; On the other hand,, will reduce the purity or the colourity of purpose product alcohol, make product alcohol can not reach the requirement of industrial salable product if some impurity not hydrogenation or incomplete hydrogenation remain in the product alcohol.
Yet, the hydrogenation of some impurity such as ester class is than the hydrogenation difficulty of aldehydes, under identical hydrogenation conditions, speed of reaction also is lower than the hydrogenation speed of aldehydes, so aldehydes and impurity are wherein all transformed fully, hydrogenation reaction often need comparatively be carried out under the exacting terms at high temperature, high pressure or the big excessive catalyzer of employing etc., and this causes the generation of some other side reaction and other problems again.For example the hydrocracking reaction at high temperature easily takes place in raw material aldehyde, generates alkanes gas, is difficult to separate with hydrogen, so can only be circulated to reactive system with hydrogen, be accumulated to the purity that to a certain degree can reduce hydrogen, hydrogenation reaction is caused disadvantageous effect, and make the hydrogen gas compressor overload easily.In addition, at high temperature, dehydration reaction easily takes place and generates ethers and water in purpose product alcohols, and alcohols, ethers and water are easy to form azeotrope, have increased the separating difficulty of product alcohol.Simultaneously, the aldehyde hydrogenation also has some heavy constituent materials such as ester class to generate easily under the high temperature, and these ester classes remain in catalyst surface, have reduced activity of such catalysts and life-span.
In order to address these problems, patent US3431311, DE3542595, CN1058770, DE1227882, DE1276618 adopt two-stage or multistage gas phase hydrogenation reaction mode, in first step reaction, the aldehyde transformation efficiency is reached more than 80%, and second stage reaction then makes aldehydes and other impurity transform fully.By this method, can obviously reduce the generation of hydrogenation byproduct hydro carbons, alcohols and ethers.But adopt the mode of gas-phase reaction, needing in order to make raw material aldehyde and product alcohol maintain gas phase state, needs higher temperature of reaction with the gasification of raw material aldehyde in the reaction process, and the product saturated alcohol behind the hydrogenation also need reclaim through condensation, and this has increased energy consumption of reaction and production cost undoubtedly.In addition, because the aldehyde gas phase hydrogenation is a strong exothermal reaction, for guaranteeing to react not temperature runaway, the liquid feeding air speed of aldehyde can only be controlled at 1.0h
-1Below, be generally 0.2～0.5h
-1, the space-time yield of hydrogenation is lower.
For overcoming above problem, reported with water to be solvent among patent US4401834, the US5059710, make some ester classes and the at high temperature first hydrolysis of ethers impurity in the raw material aldehyde generate aldehyde and alcohol, and then carry out hydrogenation reaction and improve the yield of product alcohol and the method that improves the reaction space-time yield.But the employing two-step reaction has increased facility investment.Patent US2809220, US6680414, US629318 improve on this basis, still are solvent with water, and hydrolysis and hydrogenation are finished in a reactor simultaneously, have improved the economy of reaction.Yet because the solubility limit of some aldehydes and water, the concentration of hydrogenating materials aldehyde can not be regulated arbitrarily, and the mass content of water can only be in 0～10% scope in for example above-mentioned patent raw material.The aldehyde hydrogenation belongs to strong exothermal reaction, and the content of aqueous solvent is low can't effectively remove the reaction liberated heat, causes safety problem in industrial production easily, is 0.1～10h so control the stock liquid air speed on the one hand in the patent
-1, increase the product recycle ratio on the other hand, but this has also reduced reaction efficiency.In addition, because of water and product alcohol easily form azeotrope, also increased the product separating energy consumption.And reaction conditions is still comparatively harsh in the above-mentioned patent, and temperature of reaction is still up to 150～200 ℃.
Summary of the invention
The invention provides one brand-new with mixed C
4Or Trimethylmethane is the method for the synthetic isopropylcarbinol of starting raw material, in above-mentioned all patents, all do not report the method for preparing isobutyl alcohol by methylacrolein hydrogenation, and overcome above-mentioned patent report with saturated aldehyde or unsaturated aldehyde be the shortcoming that exists in the method for the synthetic saturated alcohol of raw material " adopt two-stage or multistage gas phase hydrogenation reaction mode to prepare saturated alcohol; severe reaction conditions; space-time yield is low; impurity is many, energy consumption height; Be that one step of the solvent mode of hydrogenation reaction prepares saturated alcohol perhaps with the bigger water of thermal capacitance, severe reaction conditions, reaction efficiency is low, the mutual solubility of raw material aldehyde and aqueous solvent is poor, product easily forms azeotrope, separating energy consumption is high "; promptly adopt the liquid-phase hydrogenatin reaction process of reaction conditions gentleness; and self make the solvent of hydrogenation reaction with the product isopropylcarbinol; not only can additionally not bring impurity, and dissolve each other fully, not have azeotrope to exist in the product system; reduced the product separating difficulty, the process energy consumption is low and product purity is high yet with the raw material Methylacrylaldehyde.In addition, the raw material Methylacrylaldehyde of hydrogenation is not to derive from the hydroformylation of olefin product among the present invention, so do not contain impurity such as ester class and ethers, next step is finished in the condition of gentleness can to make hydrogenation reaction.The 3rd, the raw material that the present invention adopts is cheap and easy to get, has avoided the hydroformylation of propene route to adopt the higher propylene feedstocks of price.In a word, adopt technology of the present invention and method, the production cost of isobutanol product is lower than traditional hydroformylation of propene product isobutyric aldehyde hydrogenation method, is brand-new more competitive operational path.
The object of the present invention is to provide a kind of mixed C of producing the catalytic cracking unit by-product of oil fuel with crude refining
4Or produce the surplus C that takes out of ethene and propylene by-product from steam cracking device
4Or be operational path and the method that starting raw material prepares isopropylcarbinol with the Trimethylmethane.By three steps, can be with the C of cheapness
4Be converted into isopropylcarbinol expeditiously.This operational path has been broken isopropylcarbinol production to expensive C
3The dependence of raw material propylene, the novel technical route of having opened up a preparation isopropylcarbinol, and this operational path is simple, is easy to large-scale commercial production.
Detailed description of the Invention
A kind of mixed C by cheapness
4, take out surplus C
4Or Trimethylmethane is the method that starting raw material prepares isopropylcarbinol, it is characterized in that realizing by following three steps: (1) produces the mixed C of the catalytic cracking unit by-product of oil fuel from crude refining
4In or produce the surplus C that takes out of ethene and propylene by-product from steam cracking device
4The middle preparation iso-butylene or the trimethyl carbinol of separating perhaps prepares iso-butylene by catalytic dehydrogenation of isobutane; (2) selective oxidation under molybdenum bismuth-system compound oxide catalyst action of the iso-butylene or the trimethyl carbinol prepares Methylacrylaldehyde; (3) Methylacrylaldehyde hydrogenation under the nickel catalyst effect makes isopropylcarbinol.
Mixed C from the catalytic cracking unit by-product
4In or from the surplus C of taking out of steam cracking device by-product
4Middle isobutylene separation adopts molecular sieve adsorption, sulfuric acid absorption method, isobutene oligomerisation method, direct hydration method or methanol etherification method, preferred direct hydration method and methanol etherification method, and the iso-butylene yield and the purity that adopt these two kinds of methods to obtain are higher.
Direct hydration method is a catalyzer with acidic cation-exchange resin, heteropolyacid or Hydrogen aluminosilicate zeolite, at 30～180 ℃ of temperature, pressure 0.2～5.0MPa, 0.5～4.0 hour residence time, water and C
4Under volume ratio 1～12 condition, make mixed C
4Or take out surplus C
4In the iso-butylene hydration generate the trimethyl carbinol, the trimethyl carbinol is again by Zeo-karb or activated alumina catalyst, at 80～350 ℃ of temperature, pressure 0.1～2.0MPa and trimethyl carbinol liquid air speed 0.5～6.0h
-1Dehydration makes iso-butylene under the condition.Preferable methods is: be catalyzer with the sulfonic acid ion exchange resin, at 75～110 ℃ of temperature, pressure 1.5～2.5MPa, 0.5～2.0 hour residence time, water and C
4Under volume ratio 6～8 conditions, make mixed C
4Or take out surplus C
4Middle iso-butylene hydration generates the trimethyl carbinol, and the trimethyl carbinol is again by sulfonic acid type cation exchange resin catalyst, at 80～100 ℃ of temperature, pressure 0.2～0.5MPa, trimethyl carbinol liquid air speed 1.0～5.0h
-1Dehydration makes iso-butylene under the condition.
The methanol etherification method is to be catalyzer with acidic cation-exchange resin, Hydrogen aluminosilicate zeolite, tosic acid, will contain the mixed C of iso-butylene
4Or take out surplus C
4With methyl alcohol at 40～180 ℃ of temperature, pressure 0.1～15.0MPa, C
4Liquid air speed 1～30h
-1, reaction generates methyl tertiary butyl ether under methyl alcohol and iso-butylene mol ratio 0.5～5 condition, methyl tertiary butyl ether is again by alumina base catalyst, at 100～250 ℃ of temperature, pressure 0.1～2.0MPa, methyl tertiary butyl ether liquid air speed 1.0～10.0h
-1Cracking makes iso-butylene under the condition.Preferable methods is: be catalyzer with HZSM-5, will contain the mixed C of iso-butylene
4Or take out surplus C
4With methyl alcohol at 60～120 ℃ of temperature, pressure 0.5～1.5MPa, C
4Liquid air speed 2～15h
-1, reaction generates methyl tertiary butyl ether under methyl alcohol and iso-butylene mol ratio 1～2.5 condition, methyl tertiary butyl ether passes through Modification on Al again
2O
3Catalyzer is at 160～220 ℃ of temperature, pressure 0.2～1.0MPa, methyl tertiary butyl ether liquid air speed 2.0～6.0h
-1Cracking makes iso-butylene under the condition.
Iso-butylene also can make by the dehydrogenation of isobutane reaction.Trimethylmethane is at Pt-Sn-K/Al
2O
3Under the catalyst action at 500～650 ℃ of temperature, pressure 0.2～1.0MPa, isobutane gas air speed 200～5000h
-1Dehydrogenation prepares iso-butylene under the condition; The Pt charge capacity is 0.1～2wt% in the catalyzer, and the mol ratio of Pt and Sn is 1～2, and the mol ratio of Pt and K is 5～8.The above-mentioned iso-butylene that obtains or the trimethyl carbinol and water vapour and AIR MIXTURES after preheating, are fed composite oxide catalysts x (Mo is housed
12Bi
1.8Fe
2.0Co
7.0Sb
aPb
bYb
cW
dCe
e)/yTiO
2Fixed-bed column reactor, 250～500 ℃ of temperature, pressure 0.05～0.5MPa, the total air speed 500～6000h of material mixed gas
-1, O
2With iso-butylene mol ratio 0.5～10, carry out vapor phase catalytic oxidation prepared in reaction Methylacrylaldehyde under water vapour and iso-butylene mol ratio 1～15 condition; A=0.01～2 during composite oxide catalysts is formed, b=0.01～1.0, c=0～0.1, d=0.01～3, e=0.1～2, x and y represent Primary Catalysts and carrier TiO respectively
2Amount, y/x=0～50wt%.Preferable methods is: iso-butylene or the trimethyl carbinol and water vapour and AIR MIXTURES after preheating, are fed catalyzer 80 (Mo are housed
12Bi
1.8Fe
2.0Co
7.0Sb
0.3Pb
0.2Yb
0.1W
0.5Ce
0.5)/20TiO
2Fixed-bed reactor, 350～480 ℃ of temperature, normal pressure, the total air speed 850～2600h of material mixed gas
-1, O
2With iso-butylene mol ratio 2～6, carry out vapor phase catalytic oxidation prepared in reaction Methylacrylaldehyde under the condition of water vapour and iso-butylene mol ratio 3～8.
The Methylacrylaldehyde hydrogenation can be obtained isopropylcarbinol, concrete grammar is: the isobutanol solution and the hydrogen that with mass concentration are 5%～98% Methylacrylaldehyde feed the fixed-bed reactor that load type metal catalyst Ni-Sn/HM is housed, at 40～110 ℃ of temperature, pressure 1.0～5.0MPa, Methylacrylaldehyde air speed 0.5～5.0h
-1, H
2With carry out hydrogenation reaction under the condition of Methylacrylaldehyde mol ratio 2～20.The mass ratio of auxiliary agent Sn and active ingredient Ni is 0.001～0.8 in the Ni-Sn/HM catalyzer, preferred 0.01～0.3; The Ni mass content is 2%～40%, preferred 5%～28%.The present invention is with mixed C
4Or Trimethylmethane is that the synthetic isopropylcarbinol of starting raw material has following characteristics:
(1) provides one by mixed C
4Or Trimethylmethane is the brand-new C4 raw material operational path that starting raw material prepares isopropylcarbinol;
(2) Methylacrylaldehyde can obtain isopropylcarbinol by the liquid phase one-step hydrogenation under the condition of gentleness, reaction conversion ratio and selectivity of product height;
(3) be reaction solvent with the product isopropylcarbinol, bring new impurity, product purity height, separate easily can for the product system;
(4) raw material is cheap and easy to get, and hydrogenation reaction and product sepn process efficient are high and energy consumption is low, and the isopropylcarbinol production cost is low;
(5) reaction and separating technology are simple, and the process environmental protection is easy to large-scale production.
Embodiment
Come the present invention is further described below by embodiment, but protection domain is not limited by embodiment.
Embodiment 1
The surplus C that takes out with naphtha steam cracking device by-product
4For starting raw material prepares isopropylcarbinol, C
4The quality group of raw material becomes: iso-butylene=43.6%, and 1-butylene=27.2%, normal butane=8.4%, suitable-2-butylene=5.4%, anti--2-butylene=9.7%, Trimethylmethane=3.9%.
C with above-mentioned composition
4Cut and deionized water be respectively by reactor lower end, the upper end beds of flowing through, both reverse contacts, and catalyzer is 732 type styrene sulfonic acid type resins, deionized water and C
4The cut volume ratio is 6: 1, and the reaction mass residence time is 1.5 hours, and temperature of reaction is 90 ℃, reaction pressure 2.0MPa.Reaction back light constituent C
4Discharge by the reactor upper end; The trimethyl carbinol that generates is discharged by reactor bottom after condensation, through distillation dehydration its concentration is reached more than 95%.The hydration reaction isobutene conversion is 90.7%, and trimethyl carbinol selectivity is 99.7%.
The trimethyl carbinol that obtains is passed through styrene sulfonic acid type ion-exchange resin catalyst, at 90 ℃ of temperature, pressure 0.2MPa, trimethyl carbinol liquid air speed 2.0h
-1Carry out dehydration reaction under the condition, trimethyl carbinol transformation efficiency is 99.0%, and selective isobutene is 99.2%.
Iso-butylene and water vapour and AIR MIXTURES after preheating, are fed catalyzer 80 (Mo are housed
12Bi
1.8Fe
2.0Co
7.0Sb
0.3Pb
0.2Yb
0.1W
0.5Ce
0.5)/20TiO
2Fixed-bed reactor, at 400 ℃, normal pressure, O
2Be 4 with the iso-butylene mol ratio, water vapor and iso-butylene mol ratio are 6, the total air speed 1500h of material mixed gas
-1Carry out the selective oxidation reaction under the condition, isobutene conversion 96.2%, Methylacrylaldehyde selectivity 88.7%.
The Methylacrylaldehyde that obtains is separated purification, and to be diluted to the Methylacrylaldehyde mass concentration with isopropylcarbinol be 40%, back and hydrogen feed the fixed-bed reactor that catalyst n i-Sn/HM is housed after preheating, be 60 ℃, pressure 3.0MPa, Methylacrylaldehyde mass space velocity 0.6h in temperature of reaction
-1, H
2With the Methylacrylaldehyde mol ratio is to carry out hydrogenation reaction under 4 conditions, Methylacrylaldehyde transformation efficiency 99.7%, isopropylcarbinol selectivity 92.4%.
Embodiment 2
Produce the mixed C of the catalytic cracking unit by-product of oil fuel with crude refining
4For starting raw material prepares isopropylcarbinol, C
4Raw materials quality consists of: iso-butylene=16.8%, and 1-butylene=14.6%, normal butane=10.4%, suitable-2-butylene=6.5%, anti--2-butylene=15.2%, Trimethylmethane=35.1%.
C with above-mentioned composition
4Cut and deionized water be respectively by reactor lower end, the upper end beds of flowing through, both reverse contacts, and catalyzer is a sulfonic acid ion exchange resin, deionized water and C
4The cut volume ratio is 8: 1, and the reaction mass residence time is 2.0 hours, and temperature of reaction is 85 ℃, reaction pressure 1.5MPa.Reaction back light constituent C
4Discharge by the reactor upper end;
The trimethyl carbinol that generates is discharged by reactor bottom after condensation, reaches more than 85% through distillation dehydration concentration, and the hydration reaction isobutene conversion is 92%, and trimethyl carbinol selectivity is 99.4%.The trimethyl carbinol that obtains and water vapour and AIR MIXTURES after preheating, are fed catalyzer 80 (Mo are housed
12Bi
1.8Fe
2.0Co
7.0Sb
0.3Pb
0.2Yb
0.1W
0.5Ce
0.5)/20TiO
2Fixed-bed reactor, at 420 ℃, normal pressure, O
2Be 5 with the iso-butylene mol ratio, water vapor and iso-butylene mol ratio are 4, the total air speed 1800h of material mixed gas
-1Carry out the selective oxidation reaction under the condition, isobutene conversion 95.0%, Methylacrylaldehyde selectivity 86.2%.
The Methylacrylaldehyde that obtains is separated purification, and to be diluted to the Methylacrylaldehyde mass concentration with isopropylcarbinol be 60%, back and hydrogen feed the fixed-bed reactor that catalyst n i-Sn/HM is housed after preheating, be 50 ℃, pressure 4.0MPa, Methylacrylaldehyde mass space velocity 1.0h in temperature of reaction
-1, H
2With the Methylacrylaldehyde mol ratio is to carry out hydrogenation reaction under 10 conditions, Methylacrylaldehyde transformation efficiency 99.2%, isopropylcarbinol selectivity 91.7%.
Embodiment 3
The surplus C that takes out with naphtha steam cracking device by-product
4For starting raw material prepares isopropylcarbinol, C
4Raw materials quality consists of: iso-butylene=45.1%, and n-butene=22.8%, normal butane=6.9%, suitable-2-butylene=7.9%, anti--2-butylene=12.1%, Trimethylmethane=4.9%.
C with above-mentioned composition
4Cut and methyl alcohol feed the catalytic distillation reactor that HZSM-5 is housed according to certain flow rate, at 100 ℃, 0.8MPa, C
4Liquid air speed 5.0h
-1, methyl alcohol and iso-butylene mol ratio be to carry out etherification reaction under 2.0 conditions, isobutene conversion is 95.7%, the methyl tertiary butyl ether selectivity is 99.1%, through separate purify after methyl tertiary butyl ether purity be 99.5%.
TiO is equipped with in the methyl tertiary butyl ether feeding that obtains
2/ γ-Al
2O
3The fixed-bed reactor of catalyzer are at 200 ℃, 0.6MPa, methyl tertiary butyl ether liquid air speed 4.0h
-1Carry out scission reaction under the condition, the methyl tertiary butyl ether transformation efficiency is 98.5%, and selective isobutene is 99.2%.
Iso-butylene and water vapour and AIR MIXTURES after preheating, are fed catalyzer 80 (Mo are housed
12Bi
1.8Fe
2.0Co
7.0Sb
0.3Pb
0.2Yb
0.1W
0.5Ce
0.5)/20TiO
2Fixed-bed reactor, at 405 ℃, normal pressure, O
2Be 3 with the iso-butylene mol ratio, water vapor and iso-butylene mol ratio are 3, the total air speed 2000h of material mixed gas
-1Carry out the selective oxidation reaction under the condition, isobutene conversion 95.7%, Methylacrylaldehyde selectivity 88.8%.
The Methylacrylaldehyde that obtains is separated purification, and to be diluted to the Methylacrylaldehyde mass concentration with isopropylcarbinol be 80%, back and hydrogen feed the fixed-bed reactor that catalyst n i-Sn/HM is housed after preheating, be 80 ℃, pressure 4.0MPa, Methylacrylaldehyde mass space velocity 4.2h in temperature of reaction
-1, H
2With the Methylacrylaldehyde mol ratio is to carry out hydrogenation reaction under 4 conditions, Methylacrylaldehyde transformation efficiency 99.3%, isopropylcarbinol selectivity 91.5%.
Embodiment 4
With the Trimethylmethane is that starting raw material prepares isopropylcarbinol.
With Pt-Sn-K/Al
2O
3Be catalyzer, at 580 ℃ of temperature, pressure 0.5MPa, isobutane gas air speed 1800h
-1Carry out dehydrogenation under the condition and prepare isobutene reaction, the Trimethylmethane transformation efficiency is 52.8%, and selective isobutene is 91.7%, and iso-butylene purity can arrive 99.5% after separating.
Iso-butylene and water vapour and AIR MIXTURES after preheating, are fed catalyzer 80 (M0 are housed
12Bi
1.8Fe
2.0Co
7.0Sb
0.3Pb
0.2Yb
0.1W
0.5Ce
0.5)/20TiO
2Fixed-bed reactor, at 390 ℃, normal pressure, O
2Be 5 with the iso-butylene mol ratio, water vapor and iso-butylene mol ratio are 5, the total air speed 2100h of material mixed gas
-1Carry out the selective oxidation reaction under the condition, isobutene conversion 95.8%, Methylacrylaldehyde selectivity 89.1%.
The Methylacrylaldehyde that obtains separated to purify to mass content be 95%, with hydrogen after preheating, feed the fixed-bed reactor that catalyst n i-Sn/HM is housed, be 60 ℃, pressure 3.0MPa, Methylacrylaldehyde mass space velocity 2.8h in temperature of reaction
-1, H
2With the Methylacrylaldehyde mol ratio is to carry out hydrogenation reaction under 15 conditions, Methylacrylaldehyde transformation efficiency 99.3%, isopropylcarbinol selectivity 90.8%.
Claims (7)
1. one kind with mixed C
4Or Trimethylmethane is the method for feedstock production isopropylcarbinol, it is characterized in that this method comprises following three steps:
(1) produces refinery's mixed C of the catalytic cracking unit by-product of oil fuel from crude refining
4In or produce the surplus C that takes out of ethene and propylene by-product from steam cracking device
4The middle preparation iso-butylene or the synthetic trimethyl carbinol of separating perhaps prepares iso-butylene by catalytic dehydrogenation of isobutane;
(2) selective oxidation under molybdenum bismuth-system compound oxide catalyst action of the iso-butylene or the trimethyl carbinol prepares Methylacrylaldehyde; Iso-butylene or the trimethyl carbinol and water vapour and AIR MIXTURES after preheating, are fed composite oxide catalysts x (Mo is housed
12Bi
1.8Fe
2.0Co
7.0Sb
aPb
bYb
cW
dCe
e)/yTiO
2Fixed-bed column reactor, 250～500 ℃ of temperature, pressure 0.05～0.5MPa, the total air speed 500～6000h of material mixed gas
-1, O
2With iso-butylene mol ratio 0.5～10, carry out vapor phase catalytic oxidation prepared in reaction Methylacrylaldehyde under water vapour and iso-butylene mol ratio 1～15 condition; A=0.01 in the composite oxide catalysts component～2, b=0.01～1.0, c=0～0.1, d=0.01～3, e=0.1～2, x and y represent Primary Catalysts and carrier TiO respectively
2Amount, y/x=0～50wt%;
(3) Methylacrylaldehyde hydrogenation under the nickel catalyst effect makes isopropylcarbinol; Be that the isobutanol solution of 5～98% Methylacrylaldehyde and hydrogen feed and is equipped with in the fixed-bed reactor of load type metal catalyst Ni-Sn/HM with mass concentration, at 40～110 ℃ of temperature, pressure 1.0～5.0MPa, Methylacrylaldehyde air speed 0.5～5.0h
-1, H
2With carry out hydrogenation reaction under the condition of Methylacrylaldehyde mol ratio 2～20; The mass ratio of auxiliary agent Sn and active ingredient Ni is 0.001～0.8 in the Ni-Sn/HM catalyzer, and the Ni mass content is 2～40%.
2. the method for preparing isopropylcarbinol according to claim 1 is characterized in that the mixed C from the catalytic cracking unit by-product in the step (1)
4In or from the surplus C of taking out of steam cracking device by-product
4The middle preparation iso-butylene that separates adopts molecular sieve adsorption, sulfuric acid absorption method, isobutene oligomerisation method, direct hydration method or methanol etherification method.
3. the method for preparing isopropylcarbinol according to claim 1 and 2 is characterized in that from the mixed C of catalytic cracking unit by-product
4In or from the surplus C of taking out of steam cracking device by-product
4Middle preparation iso-butylene or synthetic trimethyl carbinol employing direct hydration method or the methanol etherification method of separating: direct hydration method is a catalyzer with acidic cation-exchange resin, heteropolyacid or Hydrogen aluminosilicate zeolite, at 30～180 ℃ of temperature, pressure 0.2～5.0MPa, 0.5～4.0 hour residence time, water and C
4Under volume ratio 1～12 condition, make mixed C
4Or take out surplus C
4In the iso-butylene hydration generate the trimethyl carbinol, the trimethyl carbinol is again by Zeo-karb or activated alumina catalyst, at 80～350 ℃ of temperature, pressure 0.1～2.0MPa and trimethyl carbinol liquid air speed 0.5～6.0h
-1Dehydration makes iso-butylene under the condition; The methanol etherification method is a catalyzer with acidic cation-exchange resin, Hydrogen aluminosilicate zeolite, tosic acid, will contain the mixed C of iso-butylene
4Or take out surplus C
4With methyl alcohol at 40～180 ℃ of temperature, pressure 0.1～15.0MPa, C
4Liquid air speed 1～30h
-1, reaction generates methyl tertiary butyl ether under methyl alcohol and iso-butylene mol ratio 0.5～5 condition, methyl tertiary butyl ether is again by alumina base catalyst, at 100～250 ℃ of temperature, pressure 0.1～2.0MPa, methyl tertiary butyl ether liquid air speed 1.0～10.0h
-1Cracking makes iso-butylene under the condition.
4. the method for preparing isopropylcarbinol according to claim 2 is characterized in that direct hydration method is catalyzer with the sulfonic acid ion exchange resin, at 75～110 ℃ of temperature, pressure 1.5～2.5MPa, 0.5～2.0 hour residence time, water and C
4Under volume ratio 6～8 conditions, make mixed C
4Or take out surplus C
4In the iso-butylene hydration generate the trimethyl carbinol, the trimethyl carbinol is again by sulfonic acid type cation exchange resin catalyst, at 80～100 ℃ of temperature, pressure 0.2～0.5MPa, trimethyl carbinol liquid air speed 1.0～5.0h
-1Dehydration makes iso-butylene under the condition; The methanol etherification method is catalyzer with HZSM-5, will contain the mixed C of iso-butylene
4Or take out surplus C
4With methyl alcohol at 60～120 ℃ of temperature, pressure 0.5～1.5MPa, C
4Liquid air speed 2～15h
-1, reaction generates methyl tertiary butyl ether under methyl alcohol and iso-butylene mol ratio 1～2.5 condition, methyl tertiary butyl ether is again by modified alumina catalyst, at 160～220 ℃ of temperature, pressure 0.2～1.0MPa, methyl tertiary butyl ether liquid air speed 2.0～6.0h
-1Cracking makes iso-butylene under the condition.
5. the method for preparing isopropylcarbinol according to claim 1 is characterized in that Trimethylmethane in the step (1) is at Pt-Sn-K/Al
2O
3Under the catalyst action at 500～650 ℃ of temperature, pressure 0.2～1.0MPa, isobutane gas air speed 200～5000h
-1Dehydrogenation prepares iso-butylene under the condition; The Pt charge capacity is 0.1～2wt% in the catalyzer, and the mol ratio 1～2 of Pt and Sn, the mol ratio of Pt and K are 5～8.
6. the method for preparing isopropylcarbinol according to claim 1, it is characterized in that method in the step (2) be with iso-butylene or the trimethyl carbinol and water vapour and AIR MIXTURES after preheating, feed composite oxide catalysts 80 (Mo be housed
12Bi
1.8Fe
2.0Co
7.0Sb
0.3Pb
0.2Yb
0.1W
0.5Ce
0.5)/20TiO
2Fixed-bed reactor, 350～480 ℃ of temperature, normal pressure, the total air speed 850～2600h of material mixed gas
-1, O
2With iso-butylene mol ratio 2～6, carry out vapor phase catalytic oxidation prepared in reaction Methylacrylaldehyde under the condition of water vapour and iso-butylene mol ratio 3～8.
7. the method for preparing isopropylcarbinol according to claim 1 is characterized in that among the catalyst n i-Sn/HM of preparing isobutyl alcohol by methylacrolein hydrogenation, the mass ratio of auxiliary agent Sn and active ingredient Ni is 0.01～0.3, and the Ni mass content is 5～28%.
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