CN105503776B - A kind of method for producing oxyalkylene - Google Patents
A kind of method for producing oxyalkylene Download PDFInfo
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- CN105503776B CN105503776B CN201410512830.2A CN201410512830A CN105503776B CN 105503776 B CN105503776 B CN 105503776B CN 201410512830 A CN201410512830 A CN 201410512830A CN 105503776 B CN105503776 B CN 105503776B
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Abstract
The invention provides a kind of method for producing oxyalkylene, this method is included in the catalytic distillation reactor with least one reaction zone, alkene is contacted in the reaction region with least one oxidant, obtain the logistics containing oxyalkylene and the logistics containing unreacted alkene, catalyst is filled with the reaction zone, the catalyst contains at least one HTS, and reaction zone the latter half or stripping zone are filled with basic resin.This method can obtain high oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization.
Description
Technical field
The present invention relates to a kind of method for producing oxyalkylene.
Background technology
Oxyalkylene is a kind of important oxygen-containing organic compound, such as propylene oxide, also known as expoxy propane
(propylene oxide, abbreviation PO), it is a kind of important basic organic chemical industry raw material, yield is only secondary in acryloyl derivative
In polypropylene.Purposes maximum PO is production PPG, to be processed further manufacturing polyurethane, it can also be used to produce purposes
Extensive propane diols.In addition, expoxy propane can be additionally used in the production of surfactant, oil field demulsifier etc..
With the extensive use of polyurethane material etc., the demand of expoxy propane is rising year by year.At present, industrial production
The technique of expoxy propane does not meet the requirement of green chemistry chemical technology especially there is drawback.Therefore, there is an urgent need to develop both by people
Economic and environment amenable production method.
The appearance of titanium-silicon molecular sieve TS-1 (US 4410501), it is oxidation of alkene epoxidation, phenol hydroxylation, keto-alcohol etc.
Open up a new way, particularly in terms of alkene epoxidation, achieve good catalytic oxidation effect.
Using hydrogen peroxide be oxidant, methanol in the reaction system of solvent, HTS has higher to propylene
Catalytic activity, at present, the technique is pushed to industrialize by Dow/BASF and Degussa/Uhde.It is but existing generally to ask
Topic is that after device operating a period of time, the activity and selectivity of catalyst can reduce, i.e., catalyst can occur in operation process
Deactivation phenomenom.The mode mainly solved at present is to make catalyst recover to live using two kinds of modes of in-situ regeneration and ex-situ regeneration
Property.Wherein, in-situ regeneration is primarily directed to the lighter situation of level of deactivation, typically using solvent and/or oxidant in a constant temperature
The lower dipping of degree rinses certain time to realize；Ex-situ regeneration is general to use primarily directed to the more serious situation of level of deactivation
The modes such as roasting are realized.Typically industrially, using first renewing catalyst activity is made through in-situ regeneration, when in-situ regeneration
After can not recovering catalyst activity, then using ex-situ regeneration.So regeneration the problem of existing is when reruning after regeneration,
When particularly being reruned after in-situ regeneration, the activity and selectivity of catalyst fluctuates larger, it is necessary to be lot more time to stabilization,
To combine simultaneously and improve the operations such as reaction temperature to realize the steady operating of reaction, but can so further speed up catalyst inactivation
And purpose product selectivity is reduced, subsequent product refining spearation is influenceed, is also unfavorable for keeping the safety in production.
CN101279959A discloses a kind of method of synthesizing epoxypropane, it is characterised in that solution ph and reaction temperature
Adjusted according to hydrogen peroxide conversion ratio in whole course of reaction, as soon as hydrogen peroxide conversion ratio is reduced to 88.5%, improved at any time
Solution ph and reaction temperature.The invention can extend the single run longevity of catalyst by adjusting solution ph and reaction temperature
Life.But this method is unfavorable for the repeated multiple times regeneration of catalyst, that is, the entire life of catalyst is influenceed, because improving reaction temperature
Afterwards, the speed of catalyst inactivation is accelerated, and this catalyst inactivated after raising temperature is not easy to carry out in-situ regeneration, and
Activity is difficult to obtain complete recovery after regeneration.
The content of the invention
It is an object of the invention to provide a kind of method of the continuous production oxyalkylene suitable for commercial Application, this method is not
It only can be carried out continuously the oxidation reaction of alkene, and the conversion ratio of high oxidant, oxyalkylene selectivity can be obtained
With oxidant effective rate of utilization.
The invention provides a kind of method for producing oxyalkylene, this method is included in urging with least one reaction zone
Change distillation reactor in, alkene is contacted in the reaction region with least one oxidant, obtain the logistics containing oxyalkylene with
And the logistics containing unreacted alkene, the reaction zone are filled with catalyst, the catalyst contains at least one titanium silicon point
Son sieve, reaction zone the latter half or stripping zone are filled with basic resin.
The method of the present invention can obtain high oxidant conversion ratio, oxyalkylene selectivity and oxidant and effectively utilize
Rate.Also, the method according to the invention is carried out in catalytic distillation reactor, alkene and oxidant are being filled with titanium silicon point
Son sieve is reacted in the reaction zone as the catalyst of active component, can make full use of reaction latent heat so that oxidation product
It can separate with raw material olefin side border ring, so as to save follow-up separation costs, realize energy-saving.Simultaneous reactions area lower half
Part or stripping zone are filled with basic resin etc., can improve oxidant conversion ratio, and then improve the security of device operation.
Brief description of the drawings
Fig. 1 is a kind of preferred embodiment of the method for the present invention.It is denoted as in figure：Oxidant storage tank 1, alkene storage tank
2nd, solvent tank 3, oxyalkylene pans 4, solvent knockout drum 5, accessory substance knockout drum 6, contain oxyalkylene and unreacted
The logistics 7 of alkene, olefin feedstocks line 8, the unreacted olefin stream 9 isolated, containing oxidized byproduct and water and solvent
Deng logistics 10, catalytic distillation reactor 11, oxyalkylene logistics 12, oxyalkylene storage tank 13.
Embodiment
The invention provides a kind of method for producing oxyalkylene, this method is included in urging with least one reaction zone
Change distillation reactor in, alkene is contacted in the reaction region with least one oxidant, obtain the logistics containing oxyalkylene with
And the logistics containing unreacted alkene, catalyst is filled with the reaction zone, and the catalyst contains at least one titanium silicon
Molecular sieve, reaction zone the latter half or stripping zone are filled with basic resin.
The method according to the invention, contact of the alkene with oxidant are carried out in the reaction region, the present invention for by alkene and
The method that oxidant is sent into reaction zone is not particularly limited.Preferably, the oxidant is sent into from first charging aperture described anti-
Area is answered, the alkene is sent into the reaction zone, the first charging aperture to the bottom of the reaction zone from second charging aperture
Theoretical cam curve is T1, the theoretical cam curve of the second charging aperture to the bottom of the reaction zone is T2, T1＞ T2.More preferably
Ground, the theoretical cam curve of the reaction zone is T, T1Percent value with T is 50-100%, T2Percent value with T is 10-
80%.It is further preferred that T1Percent value with T is 80-100%, T2(it is more preferably for 10-30% with T percent value
10-20%).
The present invention is not particularly limited for the theoretical cam curve of the reaction zone, can be conventional selection.Preferably, institute
The theoretical cam curve for stating reaction zone can be 20-45, preferably 30-40.
The method according to the invention, the catalyst are used as active component using HTS.
The HTS is the general name of a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework, can be with
With chemical formula xTiO2·SiO2Represent.The present invention is not particularly limited for the content of titanium atom in HTS, Ke Yiwei
The conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-
0.025。
The HTS can be the common HTS with various topological structures, such as：The titanium silicon
Molecular sieve can be the HTS (such as TS-1) selected from MFI structure, the HTS (such as TS-2) of MEL structures, BEA knots
The HTS (such as Ti-Beta) of structure, the HTS (such as Ti-MCM-22) of MWW structures, the titanium silicon molecule of hexagonal structure
Sieve (such as Ti-MCM-41, Ti-SBA-15), HTS (such as Ti-MOR), the HTS of TUN structures of MOR structures
One or more in (such as Ti-TUN) and the HTS of other structures (such as Ti-ZSM-48).
Preferably, the HTS is selected from HTS, the HTS and BEA of MEL structures of MFI structure
The HTS of structure.It is highly preferred that the HTS is the HTS of MFI structure, such as TS-1 molecular sieves.From
The angle for further improving the selectivity of the conversion ratio of hydrogen peroxide, the effective rate of utilization of oxidant and oxyalkylene is set out,
At least partly described HTS is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, should
The radical length of the chamber portion of hollow-core construction is 5-300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, inhale
The benzene adsorbance that measures is at least 70 milligrams per grams under conditions of the attached time is 1 hour, the nitrogen absorption under low temperature of the HTS
Hysteresis loop between adsorption isotherm and desorption isotherm be present.Herein, the HTS with the structure is referred to as hollow titanium
Si molecular sieves (HTS).The hollow HTS is commercially available (such as builds feldspathization stock commercially available from Sinopec Hunan
The molecular sieve that the trade mark of part Co., Ltd is HTS), it can also be prepared according to the method disclosed in CN1132699C.
The method according to the invention, in a preferred embodiment, the catalyst are hollow HTS HTS
And titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve catalyst are set at least to hollow HTS HTS in the reaction region
Two parts beds for active component and using titanium-silicon molecular sieve TS-1 as active component, the hollow HTS
HTS and titanium-silicon molecular sieve TS-1 the filling order in the reaction zone are the hollow HTS HTS in lower section and titanium silicon
Molecular sieve TS-1 up, so can not only further extend the catalyst stabilization duration of runs, while can also further carry
The selectivity of high oxidation alkene.In the preferred embodiment, the hollow HTS HTS and the HTS
TS-1 mass ratio can be 0.1-25：1, preferably 1-20：1.
The method according to the invention, the reaction zone the latter half or stripping zone are also filled with basic resin, so can
Obtain the conversion ratio and oxyalkylene selectivity of the oxidant further improved.The basic resin can load in a variety of manners
In the reaction zone.The amount of the basic resin can carry out appropriate selection according to the amount of catalyst.Usually, the alkali
Property resin and the catalyst weight ratio can be 0.01-0.2：1, preferably 0.05-0.1：1.
In the present invention, the basic resin is preferably alkalescence anion-exchange resin, can be well known in the art each
Kind alkalescence anion-exchange resin, including strong-base anion-exchange resin and/or weak-base anion-exchange resin.Specifically
Ground, the ion-exchange group in the deacidite can be quaternary ammonium group ,-NR3OH、-NH2,-NHR and-NR2In
One or more, wherein, R is respectively a kind of alkyl, preferably a kind of alkyl, more preferably C1-C5Alkyl.Further, institute
It for example can be that polystyrene alkalescence anion-exchange resin and/or acrylic acid series alkali anion exchange tree to state basic resin
Fat.The basic resin can be macroporous type or gel-type, preferably macroporous type.
The ion exchange capacity of the basic resin is not particularly limited, and can be conventional selection.Usually, the alkalescence
The full exchange capacity of ion exchange resin can be 0.1-10 mols/kg.The full exchange capacity is the ion of unit weight
The molal quantity of ion-exchange group contained by exchanger resin, it can be determined under conditions of GB/T8144-2008 defineds,
It can be obtained from the product information for the ion exchange resin being commercially available.Total exchange content in the embodiment of the present invention is from business
Obtained in the product information for the ion exchange resin bought.
The method according to the invention, alkene are the alkene no more than 12 carbon atoms, and preferably carbon number is 2-6 alkene
Hydrocarbon, more preferably propylene and butylene.
The method according to the invention, the oxidant can be that commonly used in the art various olefin oxidation can be formed into oxygen
Change the compound of alkene.Preferably, the oxidant (that is, contains the chemical combination of-O-O- keys selected from peroxide in molecular structure
Thing).The peroxide can be hydrogen peroxide and/or organic peroxide.Preferably, the oxidant is hydrogen peroxide.
From the angle for the security for being further ensured that the present invention, the method according to the invention preferably using existing as an aqueous solution
Hydrogen peroxide.When the hydrogen peroxide provides as an aqueous solution, the concentration of the aqueous hydrogen peroxide solution can be this
The normal concentration in field, such as：20-80 weight %.The present invention is not particularly limited for the dosage of the oxidant, Ke Yiwei
Conventional selection.Usually, the mol ratio of alkene and the oxidant can be 1：0.1-2, preferably 1：0.3-2, more preferably
1：0.8-2.
The method according to the invention, the contact with the catalyst of alkene and the oxidant is preferably at least one solvent
In the presence of carry out.The species of the solvent is not particularly limited.It is highly preferred that the solvent is selected from methanol and/or water.This hair
The bright dosage for solvent is not particularly limited, and can be conventional selection.Usually, the mass ratio of alkene and solvent can be 1：
0.5-50, preferably 1：3-15.
Steamed method according to the invention it is possible to which the solvent is sent into the catalysis using various methods commonly used in the art
In the reaction zone for evaporating reactor, so that alkene contact with the oxidant is carried out in the presence of solvent.Such as：Can be by solvent
It is sent into the reaction zone, can also be sent into from the bottom of reaction zone in the reaction zone from the top of reaction zone, can also be from
The middle part of reaction zone is sent into the reaction zone.When the solvent is sent into the reaction zone from the bottom of reaction zone, institute
Solvent is stated preferably to be admitted in the reaction zone in same position with the alkene, more preferably will be described molten by same charging aperture
Agent and oxidant are sent into the reaction zone.
The method according to the invention, the alkene can be realized alkene with the condition of the contact of the oxidant with one side
Hydrocarbon is oxidized into oxyalkylene, and on the other hand the oxyalkylene that contact generation can be defined with unreacted separation of olefins.One
As, the condition of the contact includes：Temperature can be 20-200 DEG C, preferably 30-180 DEG C, more preferably 30-120 DEG C；Return
It can be 1 to flow ratio：More than 1 (is specifically as follows 1-100：1), preferably 2：More than 1 (is specifically as follows 2-20：1)；The weight of alkene
When air speed can be 0.1-10000h-1, preferably 1-1000h-1, more preferably 2-20h-1.The reflux ratio refers to return to reaction
The ratio of the quality of material in area and the quality of material as product obtained from reaction zone.
Method according to the invention it is possible to reaction zone is heated using various methods commonly used in the art, so that institute
The temperature for stating reaction zone is enough to make alkene react with the oxidant, and can be distilled.The method according to the invention
Heating medium is not limited, reaction zone is heated to required temperature as long as can realize, preferably by alkene and/or solvent
As heating medium.That is, alkene and/or solvent are heated to being enough to make alkene react with oxidant and are enough to make generation
The temperature of oxyalkylene and separation of olefins, and the alkene with the temperature and/or solvent are sent into reaction zone.
The method according to the invention can be in the conventional various catalysis that can carry out catalytic reaction and separated simultaneously
Carried out under catalytic distillation conditions in distillation reactor.Usually, the catalytic distillation reactor can have distillation zone (connection
Tower top), reaction zone and stripping zone (connection tower reactor), the reaction zone is between the distillation zone and stripping zone.It can use
Catalyst and optional filler are seated in form reaction zone in catalytic distillation reactor, herein not by conventional various methods
It is described in detail again.
The method according to the invention, obtained at the top of catalytic distillation reactor containing oxyalkylene and unreacted alkene
Logistics.The logistics containing oxidized byproduct and water and solvent etc. is obtained from the bottom of catalytic distillation reactor.
The method according to the invention, the logistics containing oxyalkylene can be entered using method (such as rectifying) commonly used in the art
Row separation, to obtain oxyalkylene.Logistics containing unreacted alkene can isolate alkene therein using conventional method,
And the alkene isolated is fed again into reaction zone and carries out oxidation reaction.
Fig. 1 shows a kind of preferred embodiment of the method according to the invention.As shown in figure 1, preferably
In, hydrogen peroxide existing in the form of hydrogen peroxide is used as oxidant, by oxidant storage tank 1 and catalytic distillation reactor 11
Reaction zone top connection, by hydrogen peroxide be sent into reaction zone (that is, the region of the middle part shadow representation of catalytic distillation reactor 11,
Upper part is catalyst Ti-si molecular sieves, and bottom is divided into basic resin) top；By the top of solvent tank 3 and reaction zone or
Bottom (catalyst layer) is connected, and solvent is sent into the top of the reaction zone or bottom (preferably passes through solvent and oxidant same
One charging aperture is sent into reaction zone), alkene storage tank 2 is connected with the bottom of reaction zone, alkene is sent into the bottom of reaction zone；Will
Condition in catalytic distillation reactor 11 is adjusted to make oxidant that oxidation reaction occur to form oxyalkylene simultaneously with alkene
The bar for passing through separated by the oxyalkylene of generation and unreacted alkene and containing oxidized byproduct and water and solvent etc.
Part, so as to obtain the logistics 10 containing oxidized byproduct and water and solvent etc. in the bottom of catalytic distillation reactor 11, urging
The top for changing distillation reactor 11 obtains the logistics 7 containing oxyalkylene and unreacted alkene.Oxyalkylene and not will be contained
The logistics 7 of the alkene of reaction is sent into oxyalkylene pans 4 and carries out gas-liquid separation, obtains gaseous olefin logistics 9 and liquid oxygen
Change olefin stream 12, the gaseous olefin logistics 9 is sent into alkene storage tank 2；Oxyalkylene is sent into the oxyalkylene logistics 12
Storage tank 13 carries out the further processing step such as refined, so as to obtain purpose product oxyalkylene.Oxidized byproduct will be contained
(solvent is sent back to solvent is isolated for example, by the method for distillation in the feeding solvent of logistics 10 knockout drum 5 of water and solvent etc.
Storage tank 3), obtain the logistics containing oxidized byproduct and be then sent in accessory substance knockout drum 6 to be separated, so as to obtain
Oxidized byproduct.
Describe the present invention, but content not thereby limiting the invention in detail with reference to embodiments.
In embodiment and comparative example, agents useful for same is commercially available AR.
HTS (TS-1) used is by prior art Zeolites 1992 in embodiment and comparative example,
The TS-1 sieve samples that method described in the 943-950 pages of Vol.12 is prepared, its titanium oxide content are 2.5 weights
Measure %.Hollow HTS HTS produces for Hunan Jianchang Petrochemical Co., Ltd, is described in Chinese patent CN1301599A
The industrial products of HTS, exist between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS
Hysteresis loop, crystal grain are that the radical length of hollow crystal grain and chamber portion is 15-180 nanometers；The HTS sample at 25 DEG C,
P/P0=0.10, the benzene adsorbance that adsorption time measures under conditions of 1 hour is 78 milligrams per grams.Its titanium oxide content is 2.4 weights
Measure %.
Prepare the preparation that embodiment 1-4 illustrates the catalyst in the present invention.
Prepare embodiment 1
Under conditions of normal pressure (1 standard atmospheric pressure) and 40 DEG C, tetraethyl orthosilicate is added to TPAOH water
In solution, hollow HTS is added after stirring 2h and continues to stir 1h.Wherein, hollow HTS HTS, silicic acid tetrem
The mass ratio of ester, TPAOH and water is 100：350：5：120.Mixture will be obtained after spin is granulated, at 550 DEG C
5h is calcined, obtains spherical catalyst, the average grain diameter of the catalyst is 50 microns.
Prepare embodiment 2
Catalyst is prepared using with preparing the identical method of embodiment 1, unlike, hollow HTS HTS, silicic acid
The mass ratio of tetra-ethyl ester, TPAOH and water is 100：100：10：50, and obtain average grain diameter after spin is granulated and be
500 microns of spheric catalyst.
Prepare embodiment 3
Catalyst is prepared using with preparing the identical method of embodiment 1, unlike, hollow HTS HTS, silicic acid
The mass ratio of tetra-ethyl ester, TPAOH and water is 100：200：40：500, and obtain average grain diameter after spin is granulated
For 1000 microns of spheric catalyst.
Prepare embodiment 4
Catalyst is prepared using with preparing the identical method of embodiment 1, unlike, hollow HTS HTS is by titanium
Silicalite TS-1 replaces.
Embodiment 1-10 illustrates the method for the present invention
Embodiment 1
Mass ratio according to alkene and hydrogen peroxide (concentration is 27.5 weight %) and acetone is 5：1.2：15 ratio is from anti-
The throat-fed in area is answered, wherein, alkene is fed from second charging aperture (being located at reaction zone middle and lower part, similarly hereinafter), hydrogen peroxide and third
Ketone is fed from first charging aperture (being located at reaction zone middle and upper part, similarly hereinafter), and the temperature of reaction zone is 47 ± 3 DEG C, the pressure of reaction zone
For 0.15 ± 0.02MPa, the weight (hourly) space velocity (WHSV) of alkene is 2h-1, the reflux ratio in reaction zone is 5：1, the total theoretical tray of reaction zone
Number is 35, and the theoretical cam curve of first charging aperture to reaction zone bottom is 30, the theoretical tower of second charging aperture to reaction zone bottom
Plate number is 10, and catalyst and the macroporous strong basic styrene series anion exchange for preparing prepared by embodiment 1 are filled with reaction zone
Resin (is purchased from Anhui Samsung resin Co., Ltd, ion-exchange group is-N (CH3)3OH, total exchange capacity are 2.8 moles/thousand
Gram, the weight ratio of deacidite and catalyst is 0.1：1) and θ ring fillers (using the total amount of catalyst and filler as
Benchmark, the content of θ ring fillers is 40 weight %, and the mixture of θ ring fillers and catalyst is seated in into reaction zone middle and upper part, resin
It is seated in reaction zone bottom).Sampling analysis after stable operation 4h, and calculate oxidant conversion ratio, oxyalkylene selectivity and oxygen
Agent effective rate of utilization, the results are shown in Table 1.
In table 1,
Comparative example 1
Oxyalkylene is produced using method same as Example 1, unlike, it is added without resin.Oxidant conversion ratio,
Oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 2
Mass ratio according to alkene and hydrogen peroxide (concentration is 27.5 weight %) and benzene acetonitrile is 8：3.2：8.9 ratio from
The throat-fed of reaction zone, wherein, alkene is fed from second charging aperture, and hydrogen peroxide and benzene acetonitrile are fed from first charging aperture,
The temperature of reaction zone is 70 ± 5 DEG C, and the pressure of reaction zone is 0.35 ± 0.05MPa, and the weight (hourly) space velocity (WHSV) of alkene is 8h-1, reaction zone
Interior reflux ratio is 8：1, the total theoretical cam curve of reaction zone is 35, and first charging aperture is to the theoretical cam curve of reaction zone bottom
30, the theoretical cam curve of second charging aperture to reaction zone bottom is 10, is filled with reaction zone and prepares catalysis prepared by embodiment 2
Agent and θ ring fillers (on the basis of the total amount of catalyst and filler, the content of θ ring fillers is 30 weight %, by θ ring fillers with
In the reaction region, macroporous strong basic acrylic acid type anion exchange resin (wins honour for tree purchased from Hangzhou for the mixture filling of catalyst
Fat Co., Ltd, ion-exchange group are-NH2, total exchange capacity is 0.9 mol/kg), deacidite is with urging
The weight ratio of agent is 0.05：1) it is seated in stripping zone).Sampling analysis after stable operation 8h, and calculate oxidant conversion ratio, oxygen
Change olefine selective and oxidant effective rate of utilization, the results are shown in Table 1.
Embodiment 3
Mass ratio according to alkene and hydrogen peroxide (concentration is 50 weight %) and the tert-butyl alcohol is 10：1.5：10 ratio is from anti-
The throat-fed in area is answered, wherein, alkene is fed from second charging aperture, and hydrogen peroxide and the tert-butyl alcohol are fed from first charging aperture, instead
It is 60 ± 5 DEG C to answer the temperature in area, and the pressure in reaction zone is 0.25 ± 0.02MPa, and the weight (hourly) space velocity (WHSV) of alkene is 5h-1, reaction
Reflux ratio in area is 3：1, the total theoretical cam curve of reaction zone is 35, theoretical cam curve of the first charging aperture to reaction zone bottom
For 30, the theoretical cam curve of second charging aperture to reaction zone bottom is 10, and urging of preparing prepared by embodiment 3 is filled with reaction zone
Agent, gel type strong base styrene series anion exchange resin (are purchased from Shandong Dong great chemical industry Co., Ltd, ion exchange
Group is-N (CH3)3OH, total exchange capacity are 1.5 mols/kg, and the weight ratio of deacidite and catalyst is
0.2：1) and θ ring fillers (on the basis of the total amount of catalyst and filler, the content of θ ring fillers is 10 weight %, and θ rings are filled out
The mixture of material and catalyst is seated in reaction zone middle and upper part, and resin is seated in reaction zone bottom).Sampled after stable operation 12h
Analysis, and oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are calculated, it the results are shown in Table 1.
Embodiment 4
Oxyalkylene is produced using method same as Example 1, unlike, catalyst is prepared to prepare embodiment 4
Catalyst.Oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 5
Using production oxyalkylene same as Example 1, the difference is that, catalyst is that mass ratio is 1:1 preparation is real
Apply the catalyst of the preparation of example 1 and prepare catalyst prepared by embodiment 4, wherein preparing the catalyst of the preparation of embodiment 4 up.
Oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 6
Using production oxyalkylene same as Example 1, the difference is that, catalyst is that mass ratio is 1:1 preparation is real
Apply the catalyst of the preparation of example 1 and prepare catalyst prepared by embodiment 4, wherein preparing the catalyst of the preparation of embodiment 1 up.
Oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 7
Using production oxyalkylene same as Example 1, the difference is that, catalyst is mass ratio 20:1 preparation is implemented
Catalyst and prepare catalyst prepared by embodiment 4 prepared by example 1, wherein preparing the catalyst of the preparation of embodiment 4 up.Oxygen
Agent conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 8
Oxyalkylene is produced using method same as Example 1, unlike, resin is seated in carrying for reaction zone bottom
Evaporate area.Oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 9
Using production oxyalkylene same as Example 1, the difference is that, catalyst is mass ratio 1:2 preparation is implemented
Catalyst and prepare catalyst prepared by embodiment 4 prepared by example 1, wherein preparing the catalyst of the preparation of embodiment 4 up.Oxygen
Agent conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Embodiment 10
Oxyalkylene is produced using method same as Example 1, unlike, alkene is butylene.Oxidant conversion ratio,
Oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Comparative example 2
Oxyalkylene is produced using method same as Example 1, unlike, resin is seated in reaction zone top.Oxygen
Agent conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Comparative example 3
Oxyalkylene is produced using method same as Example 1, unlike, resin is seated in after being mixed with catalyst
In reaction zone.Oxidant conversion ratio, oxyalkylene selectivity and oxidant effective rate of utilization are listed in table 1.
Table 1
As can be seen from Table 1, using the present invention method produce oxyalkylene, can obtain high oxidant conversion ratio with
And oxyalkylene selectivity, while high oxidant effective rate of utilization can also be obtained；Meanwhile method of the invention is in catalytic distillation
Reacted in reactor, product separation can be carried out simultaneously, efficiently utilize caused heat in oxidation system, saved
Energy consumption.
In addition, from embodiment 5-7 and 9 data result can be seen that when the catalyst in the reaction region at least provided with
To be active component and two parts catalyst bed using titanium-silicon molecular sieve TS-1 as active component using hollow HTS HTS
Layer, the HTS and TS-1 the filling order in the reaction zone be the HTS lower section and TS-1 up when, when wherein, institute
The HTS and TS-1 mass ratio stated is 1-20：There is superior technique effect when 1.
Claims (13)
1. a kind of method for producing oxyalkylene, this method is included in the catalytic distillation reactor with least one reaction zone
In, alkene is contacted in the reaction region with least one oxidant, the logistics containing oxyalkylene is obtained and contains unreacted
Alkene logistics, be filled with catalyst in the reaction zone, reaction zone the latter half or stripping zone are filled with basic resin, its
In, the catalyst is set at least to using hollow HTS HTS as active component and with HTS in the reaction region
TS-1 is two parts beds of active component, and the hollow HTS HTS and titanium-silicon molecular sieve TS-1 are described
Filling order is the hollow HTS HTS in lower section and titanium-silicon molecular sieve TS-1 up in reaction zone, described HTS
Mass ratio with TS-1 is 1-20：1.
2. according to the method for claim 1, wherein, the contact is carried out in the presence of at least one solvent.
3. according to the method for claim 2, wherein, the solvent is sent into the reaction zone with oxidant by same charging aperture
In.
4. according to the method in claim 2 or 3, wherein, the mass ratio of alkene and the solvent is 1：0.5-50.
5. according to the method in claim 2 or 3, wherein, the solvent is selected from water, C1-C6Alcohol, C3-C8Ketone and C2-C6
Nitrile.
6. the method according to claim 1 or 3, wherein, the oxidant is sent into the reaction zone from first charging aperture,
Alkene is sent into the reaction zone, the theoretical cam curve of the first charging aperture to the bottom of the reaction zone from second charging aperture
For T1, the theoretical cam curve of the second charging aperture to the bottom of the reaction zone is T2, T1＞ T2。
7. according to the method for claim 6, wherein, the theoretical cam curve of the reaction zone is T, T1Percent value with T is
50-100%, T2Percent value with T is 10-80%.
8. the method according to claim 11, wherein, T1Percent value with T is 80-100%, T2Percent value with T is
10-30%.
9. according to the method for claim 1, wherein, the mol ratio of alkene and the oxidant is 1：0.1-2.
10. according to the method described in any one in claim 1,3 and 9, wherein, alkene is the alkene no more than 12 carbon atoms
Hydrocarbon, the oxidant are peroxide.
11. according to the method for claim 10, wherein, the alkene is propylene and butylene, and the oxidant is peroxidating
Hydrogen.
12. according to the method for claim 1, wherein, the condition of the contact includes：Temperature is 20-200 DEG C, reflux ratio
For 1-100：1, the weight (hourly) space velocity (WHSV) of alkene is 0.1-10000h-1。
13. in accordance with the method for claim 1, wherein, the weight ratio of described basic resin and the catalyst is 0.01-
0.2：1.
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