CN103804139B - The preparation method of the tert-butyl alcohol - Google Patents
The preparation method of the tert-butyl alcohol Download PDFInfo
- Publication number
- CN103804139B CN103804139B CN201210458153.1A CN201210458153A CN103804139B CN 103804139 B CN103804139 B CN 103804139B CN 201210458153 A CN201210458153 A CN 201210458153A CN 103804139 B CN103804139 B CN 103804139B
- Authority
- CN
- China
- Prior art keywords
- fixed bed
- reactor
- tert
- butyl alcohol
- bed reactors
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of the tert-butyl alcohol is disclosed, it comprises the steps: that (a) is to the aqueous solution that adds the tert-butyl alcohol in the first order of the fixed bed reactors of a plural serial stage, and it is 0.2-0.8:1 with the mass ratio of the tert-butyl alcohol that the addition of the tert-butyl alcohol aqueous solution makes the import water (referring to water and the fresh water sum adding by stoichiometry in the tert-butyl alcohol aqueous solution) of first order reactor; (b) mixing carbon four is added respectively to every one-level fixed bed reactors, the effective mass air speed of isobutene in every one-level fixed bed reactors is equated. The reactor outlet stream portions of afterbody and/or two-stage is looped back to this stage reactor import simultaneously. Reach high conversion ratio thereby make to mix isobutene in carbon four, and suppress the generation of the accessory substances such as Diisobutylene. The material of reactor outlet can be realized the separation of product through a rectifying column.
Description
Technical field
The present invention relates to a kind of method of preparing tert-butanol by isobutene hydration, the inventive method has high isobutylAlkene conversion ratio, can adopt less equipment to implement, be difficult for the side reactions such as isobutene dimerization occurring and not needingUse the advantage of surfactant.
Background technology
The tert-butyl alcohol is a kind of important chemical products, can be used as solvent, gasoline additive, organic synthesis raw materialDeng. As the raw material of producing other chemical products, the tert-butyl alcohol has two important use: 1) dehydration high purityThe isobutene of degree; 2) produce MAL through oxidation, further after oxidation, obtain methacrylic acid, methylAcrylic acid generates methyl methacrylate (MMA) with methanol esterification again.
Produce in the industrial method of the tert-butyl alcohol at isobutene and hydrate, conventionally use and mix carbon four as differentButene feedstock. Mixing carbon four is a kind of important petrochemical industry resources, mainly by n-butene, isobutene, justButane, iso-butane and butadiene composition, wherein there is most component that chemical utilization is worth and be mainly isobutene andSecondly butadiene is n-butene, normal butane and iso-butane.
Representative industrialization tert-butyl alcohol preparation method is under the existence of highly acidic resin catalyst, makesThe mixing carbon four that contains isobutene and water stream, by beds, generate uncle by addition reaction thereinButanols. A key point of this class addition reaction is that making to mix carbon four forms homogeneous dispersion or molten with waterLiquid, to improve the conversion ratio of reaction. For increasing the intersolubility of mixing carbon four and water, make reaction system reach equalMutually or approach homogeneous phase and mix, this area is conventionally added surfactant or is added as product in reaction systemThe tert-butyl alcohol.
For example, Chinese patent ZL200810016874.0 discloses at emulsifying agent RC6H5O(CH2CH2O)nHUnder the existence of (wherein R is iso-octyl, new decyl or Permethyl 99A base), adopt the mixing carbon four containing isobuteneReact with water, produce the method for the tert-butyl alcohol. Due to the existence of emulsifying agent, make to mix dissolving each other of carbon four and waterProperty is improved, and has improved the conversion ratio of reaction. Not yet reach completely and dissolve each other but mix carbon four and water,And exist in charging the ratio (water hydrocarbon ratio) of water and hydrocarbon larger, can not be complete containing surface active agent wastewaterRecycle, need the problem of intermittent discharge. In addition the method is because the use of emulsifying agent has also improved productManufacturing cost.
Chinese patent ZL98812676.1 discloses one and has made solvent with the tert-butyl alcohol, makes water and the hydrocarbon containing isobuteneThe method that (mixing carbon four) produces continuously the tert-butyl alcohol in the multistage reactor of series connection. For increasing water and mixingThe intersolubility of carbon four, the method has added a large amount of tert-butyl alcohols in reaction raw materials, and the conversion ratio of reaction canReach 80 ~ 90%. The method is by the disposable all reaction raw materials import that adds reaction system, along with what reactCarry out, the reactor motive force of afterbody or two-stage reduces gradually, causes the reaction that reaches regulation conversion ratioBody is long-pending bigger than normal, thereby has improved the manufacturing cost of the final tert-butyl alcohol.
Chinese patent ZL200410057863.9 discloses a kind of method that generates the tert-butyl alcohol, and it comprises makes to containThe hydrocarbon mixture (mixing carbon four) of isobutene and water are multiple anti-what connect under acidic solid catalyst effectAnswer in device and react, and in the end the upstream of a reactor is come by a part of tert-butyl alcohol of removing in mixtureImprove the final conversion ratio of isobutene.
Chinese patent ZL200510081359.7 discloses at the plural serial stage reactor of filling solid acid materialIn, by the mixture forming containing the hydrocarbon mixture of isobutene, the tert-butyl alcohol and water with there is lower water and tertiary fourthAlcohol content containing the hydrocarbon mixture of isobutene alternately supply with at least one reactor with obtain high space-time yield withThe tert-butyl alcohol preparation method of good selectivity.
In method described in Chinese patent ZL200410057863.9 and ZL200510081359.7, common ground isThe tert-butyl alcohol and mix carbon four and once enter reaction system entrance, as the water of reactant be add respectively each anti-Answer device. Although this can solve the intersolubility problem of mixing carbon four and the water of each Reactor inlet, two betterIt is more complicated that person all exists flow setting, and in the reactor of previous stage or two-stage, isobutylene concentration is relatively high,Easily there is the side reactions such as isobutene dimerization.
Therefore, this area also needs a kind of addition reaction by isobutene and water to manufacture the method for the tert-butyl alcohol, shouldMethod can adopt less equipment to implement, be difficult for occurring isobutyl under the prerequisite with high isobutene conversionSide reactions such as alkene dimerization and do not need to use surfactant.
Summary of the invention
A goal of the invention of the present invention is to provide a kind of addition reaction by isobutene and water and manufactures the tert-butyl alcoholMethod, the method can adopt less equipment to implement, no under the prerequisite with high isobutene conversionEasily there is the side reactions such as isobutene dimerization and do not need to use surfactant.
Therefore, one aspect of the present invention relates to a kind of method of preparation of the tert-butyl alcohol, and it comprises the steps:
(a) in the first order of the fixed bed reactors of a plural serial stage, add t-butanol solution, this tertiary fourthThe addition of alcoholic solution make first order reactor import water (comprise water in the tert-butyl alcohol aqueous solution with by insteadShould measure than the fresh water adding) with the mass ratio of the tert-butyl alcohol be 0.2-0.8:1; With
(b) isobutene is added respectively to first order fixed bed reactors and at least one fixed bed of one-level subsequentlyReactor, at least one is different in the fixed bed reactors of one-level subsequently to make first order fixed bed reactors and thisThe effective mass air speed of butylene equates.
In a better example of the present invention, the present invention relates to a kind of preparation method of the tert-butyl alcohol, it comprisesFollowing steps:
(a) in the first order of the fixed bed reactors of a plural serial stage, add t-butanol solution, this tertiary fourthThe addition of alcoholic solution makes the total Water of import of first order reactor and the mass ratio of the tert-butyl alcohol be0.2-0.8:1; With
(b) isobutene is added respectively to every one-level fixed bed reactors, make in every one-level fixed bed reactorsThe effective mass air speed of isobutene equates.
In a better example of the present invention, by the outlet material of afterbody and/or two-stage reactor separatelyPart loops back this Reactor inlet, and recycle ratio is 0.5 ~ 6.0, and preferably 0.6 ~ 2.5.
Brief description of the drawings
Further illustrate the present invention below in conjunction with accompanying drawing, accompanying drawing 1 is the reaction system of a better example of the present inventionThe schematic diagram of system.
Detailed description of the invention
1. term definition
In the present invention, the implication that term " mixes carbon four " is identical with the conventional sense of this area, refers to mainThe industrial chemicals being formed by n-butene, isobutene, normal butane, iso-butane and butadiene. Of the present invention oneIn individual better example, described mixing carbon four composed as follows:
| Component | wt% |
| Isobutene | 15-80 |
| 1-butylene | 5-20 |
| Cis-2-butene | 5-20 |
| Trans-2-butene | 5-20 |
| Normal butane | 1.0-20 |
| Iso-butane | 3-40 |
In the present invention, term " fixed bed reactors of plural serial stage " refers to end to end multiple fixingBed bioreactor, the quantity of its fixed bed reactors depends on the requirement of concrete reaction. In a reality of the present inventionIn example, the fixed bed reactors of described plural serial stage comprise 2-8 end to end multiple fixed bed reactors,Better comprise 2-5 end to end multiple fixed bed reactors, better comprise that 3-4 is individual end to end multipleFixed bed reactors.
In the present invention, term " the effective mass air speed of isobutene " refers to that upper level reactor is (if hadWords) discharging in unreacted isobutene, the isobutene in reactor feed at the corresponding levels, recycle stock (asThe words that have of fruit) in the isobutene quality summation of three strands of materials of isobutene and this stage reactor resin catalystMass ratio.
Except as otherwise noted, otherwise in the present invention, term " t-butanol solution " refers to that concentration is 80 ~ 98wt%The tert-butyl alcohol aqueous solution, better refer to that concentration is the tert-butyl alcohol aqueous solution of 84-95wt%, better refer to that concentration isThe tert-butyl alcohol aqueous solution of 86 ~ 92wt%.
Existing, taking the tert-butyl alcohol as solvent, making, mixing carbon four and water containing isobutene are multistage anti-what connectAnswer in device and react, to carry out in plant-scale tert-butyl alcohol production process, even if having large when reaction startsThe amount tert-butyl alcohol exists, and mixes carbon four still not so good with the intersolubility of water. In addition, existing containing isobuteneMix in the method for carbon four disposable chargings, in the time that reaction starts, the concentration of isobutene is high, and exothermic heat of reaction amount is large;The reaction later stage, reaction motive force declined along with the reactant concentration such as isobutene, water reduces, for reaching regulationConversion ratio, needs to increase reactor volume, extends residence time of material, and above two factors all easily cause generating differentThe accessory substance such as butene dimer, sec-butyl alcohol.
The present inventor finds after deliberation, if by isobutene classification charging (the i.e. fixed bed to be scheduled toThe mode that in reactor, the effective mass air speed of isobutene is equal adds respectively predetermined fixed bed anti-isobuteneAnswer device; Or in the equal mode of the effective mass air speed of isobutene in every one-level fixed bed reactors by isobutylAlkene adds respectively every one-level fixed bed reactors), when reaction starts, less tert-butyl alcohol amount also can make isobutylThe intersolubility of alkene and water improves, and along with the carrying out reacting, the tert-butyl alcohol constantly generates, and result is not anti-The intersolubility of the isobutene of answering, other organic component except isobutene and the isobutene newly adding and waterCan progressively improve until dissolve each other. The present invention completes on the basis of this research.
The present invention relates to a kind of commercial scale and prepare the method for t-butanol solution, its goal of the invention is to improve reactionThe intersolubility of isobutene and water in system, thus the conversion ratio of reaction improved, and suppress the pairs such as DiisobutyleneThe generation of product; The inventive method can make each stage reactor keep comparatively close reaction to push away on the one hand in additionPower, under same conversion, makes the cumulative volume of reactor relatively little.
The preparation method of the tert-butyl alcohol of the present invention comprises in the first order of the fixed bed reactors of plural serial stage and addingThe tert-butyl alcohol or t-butanol solution, the addition of this tert-butyl alcohol or t-butanol solution makes entering of first order reactorThe quality of saliva (comprising water and the fresh water adding by stoichiometry in t-butanol solution) and the tert-butyl alcoholThan 0.2-0.8:1, preferably 0.3-0.7:1, more preferably 0.4-0.6:1; Subsequently mixing carbon four is added to firstLevel fixed bed reactors and at least one fixed bed reactors of one-level subsequently, make this first order fixed bed anti-Answer device and this at least one subsequently in the fixed bed reactors of one-level the effective mass air speed of isobutene equate.
Add respectively each using the mixing carbon four containing isobutene as isobutene raw material and to mix carbon four belowLevel fixed bed reactors describe the present invention as an example in detail. But the present invention is not limited to use mixing carbonFour, it also can use for example substantially pure isobutene as reaction raw materials, and as previously described,The present invention is also not limited to mix carbon four and adds respectively every one-level fixed bed reactors, can add as long as mix carbon fourEnter first order fixed bed reactors and at least one one-level fixed bed reactors subsequently.
Therefore, the preparation method of the tert-butyl alcohol of the present invention comprises to the first order of the fixed bed reactors of plural serial stageIn add the tert-butyl alcohol or t-butanol solution, the addition of this tert-butyl alcohol or t-butanol solution makes first order reactionImport water (comprising water and the fresh water adding by stoichiometry in t-butanol solution) and the tert-butyl alcohol of deviceMass ratio 0.2-0.8:1, preferably 0.3-0.7:1, more preferably 0.4-0.6:1; To mix subsequently carbon four orSubstantially pure isobutene adds respectively every one-level fixed bed reactors, makes in every one-level fixed bed reactors differentThe effective mass air speed of butylene equates.
In a better example of the present invention, the method that the present invention prepares the tert-butyl alcohol comprises as reactantAdd respectively the multistage reactor entrance of series connection general containing isobutene mixings carbon four or substantially pure isobuteneThe afterbody of flow process and/or the outlet material of two-stage reactor loop back the entrance of this stage reactor.
In a better example of the present invention, as the isobutylene concentration of the mixing carbon four of reaction raw materials be15-30 % by weight, preferably 18-25 % by weight, now in the first order of described multistage fixed bed reactor orSecond level reactor, loops back outlet material part the import of each autoreactor, for example, and by 5-70 weightThe outlet material of %, better by the outlet material of 10-60 % by weight, better by the outlet thing of 20-50 % by weightMaterial loops back the import of each autoreactor.
Being applicable to every one-level fixed bed reactors of the multistage fixed bed reactor of the inventive method can be identical or notWith, better use identical fixed bed reactors. Applicable fixed bed reactors can be known in the artAny fixed bed reactors. Those of ordinary skill in the art is reading after content disclosed by the invention, canEasily determine applicable fixed bed reactors.
In an example of the present invention, use the fixed bed reactors that are filled with storng-acid cation exchange resinAs every one-level fixed bed reactors, by the mixing of the tert-butyl alcohol of scheduled volume (or t-butanol solution) and reactants waterThe first order reactor of the disposable fixed bed reactors that add series connection of thing, makes it subsequently successively by follow-upEach stage reactor. Another kind of reactant (containing the mixing carbon four of isobutene) passes through respectively before reactorStatic mixer adds the import of each stage reactor, and the inlet amount of each stage reactor mixing carbon four is pressed isobuteneThe equal principle of effective mass air speed determines, so arranges and can ensure that each stage reactor all remains suitable anti-Answer motive force, for afterbody and/or two-stage reactor, decrease as the water concentration of one of reactant,But according to the principle of reaction engineering, the circulation of material part can improve the conversion ratio of reactant. Therefore will be lastThe part of one-level and/or two-stage reactor outlet material loops back this Reactor inlet and ensures suitable conversionRate, recycle ratio (recycle stock and the mass ratio that flows to next equipment material) is 0.5 ~ 6.0, preferably0.6~2.5。
The storng-acid cation exchange resin that is applicable to the inventive method is without particular limitation, can be this areaThe storng-acid cation exchange resin of knowing, for example, it can use Chinese patent ZL200410057863.9 instituteThe acidic solid catalyst of stating. In a better example of the present invention, described strongly acidic cation exchange treeFat is
In a better example of the present invention, as isobutene mass concentration in the mixing carbon four of reaction raw materials be15 ~ 95%, preferably 25 ~ 80%, be more preferably 35 ~ 55%.
In a better example of the present invention, the reactor feed temperature of the first order (is for example no more than 60 DEG CRoom temperature to 60 DEG C), be preferably no more than 55 DEG C (for example room temperatures to 55 DEG C). The temperature rise of each stage reactorBe no more than 5 DEG C, be preferably no more than 3 DEG C.
In a better example of the present invention, fixed bed reactors of the present invention are suitable for macropore strong acid cation and hand overChange resin, its aperture is greater than 30nm, and exchange capacity is more than 1.2meq/mL. The loadings of resin is at different levels anti-Answer the device can be identical, also can be different.
In a better example of the present invention, by the content of isobutene in analysis mixing carbon four, regulate chargingMass ratio to 0.30 ~ 0.55 of middle water and isobutene, the material of afterbody reactor outlet is through a rectifyingTower can obtain having the t-butanol solution of using value after separating, wherein the mass concentration of the tert-butyl alcohol is84 ~ 95%, preferred mass concentration is 85 ~ 88%.
It is cold that the rectifying column tower top material relating in the inventive method can adopt recirculated water or wet air cooling to carry out condensationBut, in order to reach the economy of process, the operating pressure of tower top is set as 560 ~ 650kPa, corresponding materialTemperature is 44 ~ 52 DEG C. The operating pressure of reactor is retrodicted and is obtained by the operating pressure of tower, according to the level of reactorThe pressure drop of number and resin bed, the inlet pressure of first order reactor content is 800 ~ 1100kPa.
In a better example of the present invention, use reaction system as shown in Figure 1 to implement of the present inventionMethod. As shown in Figure 1, reaction system of the present invention comprises the fixed bed reactors 14,15 of three grades of series connectionWith 16, also comprise a rectifying column 17. When operation by water 1, come from the t-butanol solution 2 of rectifying column 17Mix mutually, form mixture 4. The mixture 4 that the tert-butyl alcohol 2 and water 1 are formed and scheduled volume are containing isobuteneAfter mixing carbon 43 and mixing in first order static mixer (not shown) with the form of mixture 5Enter first order fixed bed reactors 14, in these fixed bed reactors 14, water and the isobutyl mixing in carbon fourAlkene reaction, generates the tert-butyl alcohol.
Then, the reactant mixture in first order fixed bed reactors 14 6 is delivered to second level static mixingDevice (not shown) is mixed containing the carbon 43 that mixes of isobutene with scheduled volume in this blender, formsReacting material mixture 7, and send into second level fixed bed reactors 15. In these fixed bed reactors 15,Water and the isobutene reaction mixing in carbon four, generate the tert-butyl alcohol.
Equally, by the reactant mixture in second level fixed bed reactors 15 8, third level fixed bed reactors16 part discharging is mixed to form mixture 9 mutually, and this mixture 9 is delivered to third level static mixer (figureIn not shown), in this blender, mix containing the carbon 43 of mixing of isobutene with scheduled volume, form reaction formerMaterial mixture 10, and send into third level fixed bed reactors 16. In these fixed bed reactors 16, water withMix the isobutene reaction in carbon four, generate the tert-butyl alcohol.
Subsequently, by the outlet of third level fixed bed reactors, the material 11 except part circulation is sent into rectifying column 17Carry out rectifying separation, tower reactor obtains not containing the t-butanol solution of mixing carbon four, using part t-butanol solution asProduct 13 is exported, and it is anti-that other a part of t-butanol solution 2 is sent into first order fixed bed as reaction mediumAnswer device; Tower top obtains not moisture and mixing carbon 4 12 tert-butyl alcohol.
By analyzing the composition of each reactor outlet, control and regulate mixing carbon four chargings of above-mentioned each reactor,Make effective mass air speed taking isobutene as 0.15 ~ 0.30h-1, preferably 0.15 ~ 0.25h-1。
In a better example of the present invention, the mixing carbon four of use has lower isobutylene concentration (exampleAs, the concentration of isobutene is 15-40%, preferably 16-30%, better 17-25%), now by part theThe product circulation of one-level fixed bed reactors returns its charging aperture (as shown in the dotted line in Fig. 1), makes firstLevel fixed bed reactors also can reach suitable conversion in the case of the isobutylene concentration as reactant is lessRate.
In another better example of the present invention, the product part of third level reactor 16 is looped backThis stage reactor import, is mixed to form the third level admittedly mutually with the reactant mixture 8 of second level fixed bed reactorsThe charging 9 of fixed bed reactant mixture, makes in third level reactor dense at the water as one of reactant like thisDegree declines in obvious situation, reaches the object of raising conversion ratio thereby extends the time of staying by Matter Transfer.
In a better example of the present invention, the preparation method of the tert-butyl alcohol of the present invention comprises the steps:
(a) in the first order of the fixed bed reactors of a plural serial stage, add t-butanol solution, this tertiary fourthThe addition of alcoholic solution make first order reactor import water (comprise water in the tert-butyl alcohol aqueous solution with by insteadShould measure than the fresh water adding) with the mass ratio of the tert-butyl alcohol be 0.2-0.8:1; With
(b) isobutene is added respectively to odd level fixed bed reactors, make this odd level fixed bed reactorsThe effective mass air speed of middle isobutene equates.
In another better example of the present invention, the preparation method of the tert-butyl alcohol of the present invention comprises the steps:
(a) in the first order of the fixed bed reactors of a plural serial stage, add t-butanol solution, this tertiary fourthThe addition of alcoholic solution make first order reactor import water (comprise water in the tert-butyl alcohol aqueous solution with by insteadShould measure than the fresh water adding) with the mass ratio of the tert-butyl alcohol be 0.2-0.8:1; With
(b) isobutene is added respectively to first order fixed bed reactors and even level fixed bed reaction subsequentlyDevice, equates the effective mass air speed of isobutene in this first order and even level fixed bed reactors subsequently.
In an example of the present invention, as shown in Figure 1, by three of the stainless steel tube processing and manufacturing of DN100Individual reactor is connected successively, loads the approximately macropore strong acid cation exchanger resin of 2 ~ 4L in each reactor,The pressure of controlling reactor makes the material of the 3rd reactor outlet keep liquid phase, and each reactor feed is with differentThe mass space velocity of butylene meter is 0.15 ~ 0.30h-1, preferably 0.15 ~ 0.25h-1。
Rectifying column tower diameter is DN80, and the sieve plate with downspout is equipped with in its inside.
Further illustrate the present invention below in conjunction with embodiment.
Embodiment
In the following example, except as otherwise noted, otherwise use the mixing carbon four with composition as shown in table 1:
Table 1
| Component | wt% |
| Isobutene | 36.5 |
| 1-butylene | 13.7 |
| Cis-2-butene | 17.2 |
| Trans-2-butene | 16.2 |
| Normal butane | 0.8 |
| Iso-butane | 15.6 |
Embodiment 1
Use reaction system and the reaction process shown in Fig. 1. By the stainless steel tube processing and manufacturing by DN100Three reactors are connected successively, load the storng-acid cation exchange resin of about 3L in each reactorK2621. In the static mixer of first order fixed bed reactors, add t-butanol solution, this uncleThe addition of butanol solution make first order reactor import water (refer to water in t-butanol solution with by reactingMetering is than the fresh water sum adding) and the mass ratio of the tert-butyl alcohol be 0.5:1, by entering of first order reactorMouth temperature is adjusted to 54 DEG C, and the recycle ratio of third level reactor outlet is 1.0. Fresh water and total isobuteneCharging mass ratio is 0.5:1.1, and the inlet amount of each reactor mixing carbon four is by effective matter of each reactor isobuteneAmount air speed equates (to count 0.20h with isobutene-1) principle distribute and enter each reactor.
As a result, the outlet temperature of each reactor is respectively: 55.7 DEG C, 56.6 DEG C, 58.0 DEG C. Isobutene always turnsRate: 88.0%, in the logistics of third level reactor outlet, Diisobutylene concentration: 0.01%, sec-butyl alcohol is denseDegree: 0.02%. It is 87.1% the tert-butyl alcohol aqueous solution that tower bottom of rectifying tower obtains tert-butyl alcohol mass content.
Embodiment 2
Use the method identical with embodiment 1 to carry out isobutene and add the reaction that is shaped as the tert-butyl alcohol, but the third levelReactor No way out logistics circulation.
As a result, the outlet temperature of each reactor is respectively: 55.7 DEG C, 56.6 DEG C, 57.3 DEG C. Isobutene always turnsRate: 79.5%, in the logistics of third level reactor outlet, Diisobutylene concentration: 0.01%, sec-butyl alcohol is denseDegree: 0.02%. It is 84.0% the tert-butyl alcohol aqueous solution that tower bottom of rectifying tower obtains tert-butyl alcohol mass content.
Comparative example 1
Use reaction system shown in the drawings, but will mix through static state containing isobutene mixing carbon four and water, the tert-butyl alcoholClose device and mix the rear disposable first order Reactor inlet that adds, third level reactor outlet carries out logistics circulation.The inlet temperature of first order reactor is adjusted to 54 DEG C, and the charging mass ratio of fresh water and total isobutene is0.5:1.1。
As a result, the outlet temperature of each reactor is respectively: 60 DEG C, 62.8 DEG C, 64.5 DEG C. Isobutene always transformsRate: 83.4%, in the logistics of third level reactor outlet, Diisobutylene concentration: 0.30%, sec-butyl alcohol concentration:0.25%. It is 85.5% the tert-butyl alcohol aqueous solution that tower bottom of rectifying tower obtains tert-butyl alcohol mass content.
Embodiment 3
Use the mixing carbon four of composition shown in following table 2 as the isobutene raw material of the present embodiment:
Table 2
| Component | wt% |
| Isobutene | 18.5 |
| 1-butylene | 16.7 |
| Cis-2-butene | 20.2 |
| Trans-2-butene | 19.2 |
| Normal butane | 0.8 |
| Iso-butane | 17.6 |
Use reaction system and the reaction process shown in Fig. 1. By the stainless steel tube processing and manufacturing by DN100Three reactors are connected successively, load the storng-acid cation exchange resin of about 3L in each reactorK2621. In the static mixer of first order fixed bed reactors, add the tert-butyl alcohol aqueous solution, shouldThe addition of the tert-butyl alcohol aqueous solution make first order reactor import water (refer to water in the tert-butyl alcohol aqueous solution withThe fresh water sum adding by stoichiometry) with the mass ratio of the tert-butyl alcohol be 0.5:1. The first order is reactedThe inlet temperature of device is adjusted to 54 DEG C, and the recycle ratio of third level reactor outlet is adjusted to 1.0, first order reactionThe recycle ratio of device outlet is similarly 1.0. The charging mass ratio of fresh water and total isobutene is 0.5:1.1, each anti-Answer the inlet amount of device mixing carbon four to equate (to count with isobutene by the effective mass air speed of each reactor isobutene0.18h-1) principle distribute and enter each reactor.
As a result, the outlet temperature of each reactor is respectively: 54.9 DEG C, 55.5 DEG C, 56.3 DEG C. Isobutene always turnsRate: 86.8%, in the logistics of third level reactor outlet, Diisobutylene concentration: 0.008%, sec-butyl alcohol is denseDegree: 0.015%. It is 86.8% the tert-butyl alcohol aqueous solution that tower bottom of rectifying tower obtains tert-butyl alcohol mass content.
Embodiment 4
Use the isobutene of 99.5wt% as the raw material of the present embodiment.
Use reaction system and the reaction process shown in Fig. 1. By the stainless steel tube processing and manufacturing by DN100Three reactors are connected successively, load the storng-acid cation exchange resin of about 3L in each reactorK2621. In the static mixer of first order fixed bed reactors, add the tert-butyl alcohol aqueous solution, shouldThe addition of the tert-butyl alcohol aqueous solution make first order reactor import water (refer to water in the tert-butyl alcohol aqueous solution withThe fresh water sum adding by stoichiometry) with the mass ratio of the tert-butyl alcohol be 0.5:1. The first order is reactedThe inlet temperature of device is adjusted to 52 DEG C, and the recycle ratio of third level reactor outlet is adjusted to 0.8, and fresh water is with totalThe charging mass ratio of isobutene be 0.5:1.1, the inlet amount of each reactor mixing carbon four is by each reactor isobutylThe effective mass air speed of alkene equates (0.25h-1) principle distribute and enter each reactor.
As a result, the outlet temperature of each reactor is respectively: 55.0 DEG C, 56.5 DEG C, 57.4 DEG C. Isobutene always turnsRate: 90.0%, in the logistics of third level reactor outlet, Diisobutylene concentration: 0.012%, sec-butyl alcohol is denseDegree: 0.018%. It is 87.9% the tert-butyl alcohol aqueous solution that tower bottom of rectifying tower obtains tert-butyl alcohol mass content.
Embodiment 5
Use the reaction system shown in Fig. 1, only add reactor 14 and reactor 16 but mix carbon 43.Three reactors of the stainless steel tube processing and manufacturing by DN100 are connected successively, and in each reactor, filling approximatelyThe storng-acid cation exchange resin of 3LK2621. Static state at first order fixed bed reactors is mixedClosing in device adds t-butanol solution, the addition of this t-butanol solution that the import water of first order reactor (is referred toWater in t-butanol solution and the fresh water sum adding by stoichiometry) with the mass ratio of the tert-butyl alcohol be 0.5:1, the inlet temperature of first order reactor is adjusted to 54 DEG C, the recycle ratio of third level reactor outlet is 1.0.The charging mass ratio of fresh water and total isobutene is 0.5:1.1, and reactor 14 and reactor 16 mix carbon fourInlet amount by the effective mass air speed of these two reactor isobutenes equate (count 0.23h with isobutene-1）Principle distribute.
As a result, the outlet temperature of each reactor is respectively: 56.2 DEG C, 57.5 DEG C, 60.4 DEG C. Isobutene always turnsRate: 87.6%, in the logistics of third level reactor outlet, Diisobutylene concentration: 0.016%, sec-butyl alcohol is denseDegree: 0.024%. It is 86.9% the tert-butyl alcohol aqueous solution that tower bottom of rectifying tower obtains tert-butyl alcohol mass content.
Claims (10)
1. a method for the preparation of the tert-butyl alcohol, it comprises the steps:
(a) in the first order of the fixed bed reactors of a plural serial stage, add t-butanol solution, it is 0.2-0.8:1 that the addition of this t-butanol solution makes the import water of first order reactor and the mass ratio of the tert-butyl alcohol; With
(b) isobutene is added respectively to first order fixed bed reactors and at least one fixed bed reactors of one-level subsequently, make first order fixed bed reactors and this at least one subsequently in the fixed bed reactors of one-level the effective mass air speed of isobutene equate.
2. a preparation method for the tert-butyl alcohol, it comprises the steps:
(a) in the first order of the fixed bed reactors of a plural serial stage, add t-butanol solution, it is 0.2-0.8:1 that the addition of this t-butanol solution makes the total Water of import of first order reactor and the mass ratio of the tert-butyl alcohol; With
(b) isobutene is added respectively to every one-level fixed bed reactors, the effective mass air speed of isobutene in every one-level fixed bed reactors is equated.
3. method as claimed in claim 1 or 2, is characterized in that the outlet material of afterbody and/or two-stage reactor partly to loop back this Reactor inlet separately, and recycle ratio is 0.5 ~ 6.0.
4. method as claimed in claim 3, is characterized in that recycle ratio is 0.6 ~ 2.5.
5. method as claimed in claim 1 or 2, is characterized in that the reactor feed temperature of the first order is no more than 60 DEG C, and the temperature rise of each reactor is no more than 5 DEG C.
6. method as claimed in claim 1 or 2, is characterized in that adding t-butanol solution to the first order, and it is 0.3-0.7:1 that the addition of this t-butanol solution makes the import total Water of first order reactor and the mass ratio of the tert-butyl alcohol.
7. the method as described in any one in claim 1-6, it is characterized in that using and mix carbon four as reaction raw materials, the isobutylene concentration of described mixing carbon four is 15-30 % by weight, at the first order or the second level reactor of described multistage fixed bed reactor, outlet material part is looped back to the import of each autoreactor.
8. method as claimed in claim 7, is characterized in that the outlet material of 5-70 % by weight to loop back the import of each autoreactor.
9. method as claimed in claim 7, is characterized in that the outlet material of 10-60 % by weight to loop back the import of each autoreactor.
10. the method for claim 1, it is characterized in that at step (b), isobutene is added respectively to first order fixed bed reactors and odd level subsequently or even level fixed bed reactors, the effective mass air speed of isobutene in the fixed bed reactors of first order fixed bed reactors and this odd level or even level is equated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210458153.1A CN103804139B (en) | 2012-11-14 | 2012-11-14 | The preparation method of the tert-butyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210458153.1A CN103804139B (en) | 2012-11-14 | 2012-11-14 | The preparation method of the tert-butyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103804139A CN103804139A (en) | 2014-05-21 |
| CN103804139B true CN103804139B (en) | 2016-05-11 |
Family
ID=50701582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210458153.1A Active CN103804139B (en) | 2012-11-14 | 2012-11-14 | The preparation method of the tert-butyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804139B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558605A (en) * | 2018-07-13 | 2018-09-21 | 淄博齐翔腾达化工股份有限公司 | The technique and device of preparing tert-butanol by isobutene hydration |
| CN110759801B (en) * | 2018-07-27 | 2022-12-27 | 中国石油化工股份有限公司 | Method for producing diisobutylene by mixing C4 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603290A (en) * | 2003-08-22 | 2005-04-06 | 奥克森诺奥勒芬化学股份有限公司 | Process for the preparation of tert.-butanol |
| CN1670006A (en) * | 2004-03-15 | 2005-09-21 | 中国科学院大连化学物理研究所 | Process for producing lower alcohol by direct hydration of low carbon olefin |
-
2012
- 2012-11-14 CN CN201210458153.1A patent/CN103804139B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603290A (en) * | 2003-08-22 | 2005-04-06 | 奥克森诺奥勒芬化学股份有限公司 | Process for the preparation of tert.-butanol |
| CN1670006A (en) * | 2004-03-15 | 2005-09-21 | 中国科学院大连化学物理研究所 | Process for producing lower alcohol by direct hydration of low carbon olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103804139A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5757934B2 (en) | Process for producing α, β-unsaturated C10 aldehyde | |
| CN100358852C (en) | Process for the preparation of tert.-butanol | |
| CN104262196B (en) | A kind of Ammoximation reaction and separation coupling technique and device | |
| CN110759801B (en) | Method for producing diisobutylene by mixing C4 | |
| CN103804139B (en) | The preparation method of the tert-butyl alcohol | |
| CN104710295B (en) | A kind of continuous catalysis ozone oxidation cinnamic aldehyde is the preparation method of benzaldehyde | |
| CN103086828B (en) | The method of volume increase divinyl | |
| CN104812730A (en) | Method for preparing methylol alkanal | |
| CN101381283A (en) | Method for continuously preparing 3-methyl-2-butenol | |
| CN1020411C (en) | Mixed phase catalysis reaction distillation technology and equipment | |
| CN103785482B (en) | A kind of deactivating process for the treatment of of olefin isomerization catalyst | |
| CN114105735A (en) | Preparation method and production device of Guerbet alcohol ether | |
| CN105254464A (en) | Synthetic method of 1,9-decadiene | |
| CN1787982A (en) | Process for producing liquid and, optionally, gaseous products from gaseous reactants | |
| CN211123731U (en) | Intelligent control reaction system for preparing ethylene glycol based on ethylene hydration method | |
| CN104870416A (en) | Method for the catalytic aldol condensation of aldehydes | |
| CN102464633B (en) | Synthetic method for (methyl) glycidyl acrylate | |
| CN104529730B (en) | A kind of method being prepared propione by 2-amylene | |
| CN105582933B (en) | Catalyst for double-bond isomerization | |
| CN1137769C (en) | Synthesizing slurry-bed reactor | |
| CN103508885B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN106995359A (en) | A kind of isobutene polymerisation prepares the method and device of triisobutylene sum | |
| CN101704742B (en) | Reactor for producing aromatic carboxylic acid | |
| CN105503529B (en) | Method for preparing ethyl glycol by hydrolysis of ethylene carbonate | |
| KR102283565B1 (en) | Multi-compartment continuous stirring hydration reactor and method for preparating 2-Butyl alchol using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170120 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |