CN1071590C - Catalytic distillation process - Google Patents
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- CN1071590C CN1071590C CN98102726A CN98102726A CN1071590C CN 1071590 C CN1071590 C CN 1071590C CN 98102726 A CN98102726 A CN 98102726A CN 98102726 A CN98102726 A CN 98102726A CN 1071590 C CN1071590 C CN 1071590C
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Abstract
The present invention relates to a catalytic distillation process of a suspension bed. A solid catalyst and a first kind of liquid reaction materials enter a reaction distillation tower from the top of a reaction section after being ultrafinely ly homogenized and countercurrent contact a second kind of reaction materials entering from the bottom of the reaction section to carry out reaction, and then the catalyst and a liquid-phase product are directly used or regenerated in a circulating mode after being separated through a catalyst separator. The catalytic distillation process can be realized in an ordinary distilling tower without the need of using catalyst members, almost and completely eliminates the influence of the inward and outward diffusion of the catalyst, and can be used for all reaction systems suitable for adopting the ordinary reaction distillation technique.
Description
The present invention is a kind of reaction distillation technology, more particularly, is a kind of catalytic distillation technology that adopts solid acid or solid base heterogeneous catalysis.
The combination of chemical reaction process and separated process has produced reactive distillation technology.In the reaction distillation process, if adopt homogeneous catalyst then to be called the homogeneous reaction distillation, if adopt the solid heterogeneous catalyst then to be called catalytic distillation.Their common characteristic are: catalytic reaction process and separated process are carried out simultaneously in same tower and are mutually promoted, thereby all show the conversion ratio height of reaction, and selectivity is good, and advantages such as energy consumption and investment are saved in operation easily.Reactive distillation technology has obtained to use in kinds of reaction and separation process at present, wherein the successfully industrialization of process of synthetic MTBE of catalytic distillation and isopropylbenzene.
Homogeneous reaction distillation and catalytic distillation respectively have pluses and minuses.Liquid acid catalyst is adopted in the homogeneous reaction distillation, and the operation of its reactive distillation column and common destilling tower is approaching, and process is simple, but adopts liquid acid catalyst (as AlCl
3, H
2SO
4, HF etc.) and have corrosivity, can cause problems such as equipment corrosion contaminated environment, and catalyst and product separation difficulty.
Catalytic distillation adopts solid acid catalyst and is fixed in the reactive distillation column, problems such as existing corrosivity of liquid acid catalyst and separation difficulty have been avoided, make " catalyst structure " but catalyst need be carried out extra package with packing material, could in a particular manner catalyst be seated in the reaction tower.This type of feed has been brought many problems: at first, all inconvenience of the making of catalyst structure, loading and unloading is wasted time and energy.Secondly, catalyst is fixed in the tower, and there is life problems in catalyst, so needs the regeneration of stopping behind the catalysqt deactivation.At last, catalytic component is difficult to be evenly distributed in the member, has mass transfer problems such as diffusion and channel inevitably.The existence of the problems referred to above has influenced applying of catalytic distillation technology.Although domestic and international in recent years many petrochemical corporation (complex)s and research institution all once were devoted to the development of new catalyst member, and existing tens of kinds of new catalyst member patents appearance, as USP4,215,011; USP4,443,559; USP5,266,546; USP5,308,451; USP5,431,890; EP466,954; EP476,938; EP547,939; CN1048987; CN1051869; CN1076397; CN1116132; CN1127480 etc., but do not find the satisfied way of dealing with problems so far as yet.
For fear of traditional the problems referred to above that catalytic distillation technology brought, USP5 has proposed a kind of new technology that benzene and alkene carry out the alkylating ReactionDistillation of being called TM that is used in 019,669 and USP5,118,872.This technology is divided into two parts with distillation column reactor, the catalyst separator of connecting therebetween, what load in the distillation column reactor only is the distillation member (being filler) of inertia, catalyst is then made slurries in advance with benzene feedstock, enter reactor with benzene, and under the carrying secretly of benzene by being filled with the conversion zone of inertia distillation member, enter at last and recycle after catalyst separator and the fluid separation applications or regenerate.This technology has fundamentally been avoided the problem that catalyst structure brought, and catalyst can cyclic regeneration outside device.But catalyst and reaction raw materials benzene are made slurries, because big (＜10 μ m～0.5cm) of catalyst (what select for use in the patent is molecular sieve and ion exchange resin) particle, not only in tower, be difficult to be evenly distributed, and be deposited on easily on the filler and cause pressure drop excessive even stifled tower phenomenon occurs.Owing to do not provide instantiation in the patent, can this process be stablized enforcement and have no way of learning.In addition, this process is the reactor separated into two parts, middle series connection one catalyst separation device, and this makes the operation of process seem comparatively complicated.
Purpose of the present invention promptly provides a kind of catalysis member that neither needs on the basis of above-mentioned prior art, can get rid of the catalytic distillation technology of stifled tower of catalyst and diffusion couple reaction influence again.
The present invention is to provide a kind of suspension bed catalytic distillation technology between common homogeneous reaction distillation and heterogeneous catalysis distillation.
Suspension bed catalytic distillation technology provided by the invention is that solid catalyst and first kind of liquid reactions material are entered reactive distillation column by the top of conversion zone behind fine homogenizing, react with the second kind of reaction mass counter current contacting that enters from the conversion zone bottom, catalyst directly recycles after catalyst separator is separated with liquid product or regenerates.
In conjunction with the accompanying drawings, technology provided by the invention is to implement like this: solid catalyst and first kind of liquid reactions material (A) are entered in the tower by the top of the conversion zone (3) of reactive distillation column (2) behind the fine homogenizing in fine homogenizing device (1), descend with the material that gets off from overhead reflux along tower, and react with second kind of reaction mass (B) counter current contacting that enters from the conversion zone bottom.Product, remaining reactants material that reaction is generated and catalyst continue along tower and under leave conversion zone and enter tower still (5) through stripping section (4).Most of reaction mass is carried and is heated up in a steamer back conversion zone in stripping section.Because the tower still is equivalent to a theoretical plate, thereby the mixture that enters product, catalyst and a spot of residual reactant material in the tower still also can heat up in a steamer and carries out mutual further reaction (as the transalkylation reaction of benzene in alkylation process and many alkylates) through carrying once more.The material that is flowed out by the tower still enters catalyst separator (6), and isolated catalyst can be recycled or sent for regeneration, and liquid product can adopt common distillation separation method to separate.
For institute's calorific requirement is provided to stripping section, tower still reboiler (7) can be set.
Lower or when having the by product of light component to generate when the product boiling point that generated of reaction, it is just can be most of up and enter distilling period (8) along tower that these products and light component leave conversion zone, and the condensation through tower item condenser (9) enters cat head basin (10).Condensed fluid in the basin both can reflux and return distilling period, also can the product form go to carry out separated.
For decomposition reaction, oligomerisation reaction, can there be second kind of reactant (B), have only first kind of reactant (A) to react.
The catalyst that is used for technology of the present invention can be the various solid catalysts that carry out of catalytic reaction effectively, as long as catalyst is insoluble to reaction system (comprising reactant, intermediate product, product, by product etc.).Usually the solid catalyst that adopts comprises solid acid catalyst and solid base catalyst.Solid acid catalyst is various cationic ion-exchange resins, inorganic oxide, clay, heteropoly acid or its salt, various solid super acid catalyst and molecular sieve such as ZSM-5, Y, β etc.The preferred solid acid catalyst of the present invention is the heteropllyacids catalyst, comprises heteropoly acid or its salt of load or not load.Solid base catalyst comprises various anion exchange resin, hydrotalcite.
It is that catalyst granules is attenuated that catalyst enters the purpose of carrying out the fine homogenizing operation before the reactive distillation column, make it under suitable disturbance, just can be evenly dispersed in the reaction mass, can continuous-flow in tower and can not block up tower, the fine size of catalyst can also be eliminated inside and outside diffusion influence, improves the efficient of catalyst.But the granularity of catalyst can not be meticulous, and meticulous catalyst can increase the difficulty that catalyst separates with product.The appropriate catalyst granularity is 0.01～10 μ m, is preferably 0.01 μ～1 μ m.Fine homogenizing equipment can adopt various high pressure fine homogenizing devices (all there are this series products in German AKW company and Denmark APVRANNIE MS company) or various emulsification pretreatment machine.
Each of reactive distillation column that is used for technology of the present invention is partly identical with common destilling tower, need not particular design, manufacturing and operation.Reactive distillation column according to the reaction type that is carried out in the tower, product and by product situation except that conversion zone and stripping section are set routinely, distilling period (for example cat head goes out under the situation of product in the esterification of acetate and ethanol) can be set as required, distilling period (for example cat head does not go out under the situation of product in the alkylated reaction of benzene and propylene) also can be set.Each Duan Jike installs various column plates also can load the distillation filler, also can load in mixture column plate and distillation filler.In order to prevent to stop up, the most suitable plate column is sieve-plate tower and spray tower.As adopt packed tower, and filler should be greater than 1000 with the catalyst particle size ratio, and the voidage of filler answers＞70%.The number of plates of distilling period, conversion zone and stripping section or packed height are with system, the catalyst activity height of reaction, become with the requirement that separates conversion ratio.Usually distilling period should have 0～10 theoretical plate, and conversion zone should have 1～30 theoretical plate, and stripping section should have 1～20 theoretical plate.
Related performance variable comprises operating pressure, the temperature of tower, catalyst concentration, the charge ratio of raw material A and B, overhead reflux amount etc. in the technology of the present invention.Normally used tower is pressed and is normal pressure～30atm, and corresponding this pressure, tower still temperature are 100～300 ℃, and the conversion zone temperature is 85～250 ℃, and the temperature of stripping section and distilling period is the bubble point temperature under the reaction condition, and tower top temperature is 80～200 ℃.The charge ratio of raw material A and B is 1: 0～1, is preferably 1: 0.05～1, and charge ratio is to be applicable to decomposition reaction, oligomerisation reaction under 1: 0 the situation.The overhead reflux ratio be 1: 1 to infinite reflux, do not go out product as cat head, preferably adopt total reflux operation.
The bottoms material separates with catalyst, can adopt various liquid-solid isolation technics, as filtration, sedimentation, evaporation, cyclonic separation, film separation etc.
Specify suspension bed catalytic distillation technology provided by the invention with three kinds of embodiments below.
One of embodiment: reactive distillation column is only established conversion zone and stripping section, and does not establish distilling period, and this is applicable to that cat head does not go out the situation of product, employing total reflux operation, for example system of reacting for benzene alkylation with propylene.
In this embodiment, solid acid catalyst and benzene (A) are entered in the tower by the top of the conversion zone (3) of reactive distillation column (2) behind the fine homogenizing in fine homogenizing device (1), descend with the benzene that gets off from overhead reflux along tower, and react with propylene gas (B) counter current contacting that enters from the conversion zone bottom.Isopropylbenzene, a spot of diisopropylbenzene (DIPB) and the polyisopropylbenzene that reaction is generated, excessive benzene and catalyst continue along tower and under leave conversion zone and enter tower still (5) through stripping section (4).Part benzene in the conversion zone is sailed against the current simultaneously, refluxes to conversion zone through overhead condenser (9) and cat head basin (10).Entering most of benzene in the stripping section is carried and is heated up in a steamer back conversion zone.Enter material flow in the tower still through stripping section, in stripping section and tower still, can both carry out the transalkylation reaction of diisopropylbenzene (DIPB) and polyisopropylbenzene and generate purpose product isopropylbenzene.Stripping section institute calorific requirement is supplied with by tower still reboiler (7).The material that is flowed out by the tower still enters catalyst separator (6), and isolated catalyst or be directly used in recycles, or sent for regeneration, and isolated liquid product then goes separated further.
Two of embodiment: reactive distillation column is established distilling period, conversion zone and stripping section simultaneously, and this is applicable to that cat head goes out the situation of product, for example for the system of the esterification of acetate and ethanol.
In this embodiment, solid acid catalyst and acetate (A) are entered in the tower by the top of the conversion zone (3) of reactive distillation column (2) behind the fine homogenizing in fine homogenizing device (1), in tower, descend, and react with ethanol (B) counter current contacting that enters from the conversion zone bottom along tower.Owing to carry out simultaneously in conversion zone reaction and separation process, product is in case conversion zone can be in time left in generation, and the therefore restriction that can break the chemical thermodynamics balance makes reaction be tending towards complete.Be under 1: 1 the situation at acetate and ethanol raw materials components mole ratio, acetate and the full consumption of ethanol multipotency.The purpose product ethyl acetate boiling point of reaction is minimum, separates with ethanol through distilling period (8), enters cat head basin (10) through cat head cooler (9) again, and portion returns reactive distillation column as reflux, partly as the product extraction.Another product water boiling point of reaction is higher, and carrying catalyst secretly and entering tower still (5) through stripping section (4), and from the extraction of tower still.The material that is flowed out by the tower still enters catalyst separator (6) with water and catalyst separation, and catalyst can be recycled or sent for regeneration.
Three of embodiment: reactive distillation column is established distilling period, conversion zone and stripping section simultaneously, but conversion zone is only established the charging aperture of top reactant (A), and the charging aperture of reactant (B) bottom not establishing, this is applicable to the situation of having only a kind of reactant and cat head to go out product, for example for the system of MTBE decomposition reaction.
In this embodiment, solid acid catalyst and MTBE (A) are entered in the tower by the top of the conversion zone (3) of reactive distillation column (2) behind the fine homogenizing in fine homogenizing device (1) and react.Owing to carry out simultaneously in conversion zone reaction and separation process, product is in case conversion zone can be in time left in generation, and the therefore restriction that can break the chemical thermodynamics balance makes reaction be tending towards complete.The isobutene that boiling point is lower enters cat head basin (10) through distilling period (8), cat head cooler (9) successively, and part is returned reactive distillation column as reflux, partly as the product extraction.The higher methyl alcohol of boiling point is being carried catalyst secretly and is being entered the tower still through stripping section, and from the extraction of tower still.Tower kettle product enters catalyst separator with methyl alcohol and catalyst separation, and catalyst can be recycled or sent for regeneration.
Suspension catalytic distillation technology provided by the present invention has following advantage:
(1) this technology can be used for the reaction system that all are suitable for adopting the common response distillation technique, as etherificate, ether decomposition, esterification, ester hydrolysis, ester exchange, alkylation, hydration, dehydration, polycondensation, alkene oligomerization, polymerization or the like.
(2) this technology has embodied the characteristics of catalytic distillation basically, reacts in distillation, and the conversion ratio of reaction and selectivity are improved, and the heat of reaction all is used for distillation.
(3) reactive distillation column of this process using and common destilling tower are identical, and distilling period, conversion zone, this three part-structure of stripping section are in full accord, so the design of tower, operation and control all are easier to.
(4) mode of employing catalyst continuous-flow in tower, the inconvenience of having avoided catalyst structure to make and load and unload, and also catalyst can cyclic regeneration outside device.
(5) adopt solid acid catalyst to avoid the corrosion and the pollution problem of homogeneous liquid acid catalyst.
(6) the minimum catalyst of this process using particle has almost completely been eliminated inside and outside diffusion influence, has improved the utilization rate and the reaction efficiency of catalyst greatly; On the other hand, although catalyst granules is very thin, solid catalyst is more much easier with separating of product than homogeneous catalyst with separating of product.
(7) when using solid acid catalyst, this optimal process heteropllyacids catalyst, such catalyst is the novel environmental friendliness solid acid catalyst of developing in recent years of a class, be characterized in the low temperature active height, can be under normal pressure, under the boiling point of reactant, react, can reduce equipment investment and operating cost greatly thus.
Accompanying drawing is the schematic flow sheet of technology of the present invention, and among the figure: A is first kind of liquid reactants; B is second kind of reactant; 1 is the fine homogenizing device; 2 is reactive distillation column; 3 is conversion zone; 4 is stripping section; 5 is the tower still; 6 is catalyst separator; 7 is tower still reboiler; 8 is distilling period, and 9 is overhead condenser; 10 is the cat head basin.
Below will further suspension bed catalytic distillation technology provided by the invention be illustrated by the instantiation of benzene alkylation with propylene reaction, but not thereby limiting the invention.
Example 1～5
These example explanations this implementation of processes effect under the catalyst different amounts.
Adopting an internal diameter is the 34mm glass tower of vacuum silver insulation jacket in addition, all fills with φ 4 stainless steel Dixon ring fillers in the tower.Reaction segment length 1m between benzene and the propylene feed mouth, the long 0.5m of stripping section that the propylene feed mouth is following, because cat head does not go out product, thus need not establish distilling period, and adopt total reflux operation.The tower still adopts the heating of electrical heating cover, and each position temperature is listed in table 1 in the tower, and the logical running water of overhead condenser carries out condensation.With silicon dioxide carried phosphorus heteropoly tungstic acid is catalyst, and the load capacity of phosphorus heteropoly tungstic acid is 28%.Catalyst mixes with benzene, behind high-shear emulsion machine (prestige space dynamo-electric Co., Ltd in Shanghai produces) fine homogenizing (average diameter of measuring catalyst through SEM is 0.5～1 μ m), squeeze into reaction tower with the speed of 5mL/min from the top of conversion zone with peristaltic pump, propylene bottom from conversion zone after the pressure reducing flow stable metering enters reaction tower.Benzene feed alkene ratio is 1.75: 1, and infinite reflux benzene is 6: 1 with the ratio of benzene feed.
The result of the test of catalyst different content is listed in table 1.
In the table: isopropylbenzene selectivity=isopropylbenzene/(isopropylbenzene+diisopropylbenzene (DIPB)+polyisopropylbenzene) * 100%
Table 1
| Example | 1 | 2 | 3 | 4 | 5 | |
| Reaction temperature ℃ | Cat head middle part tower still | 80 81 96 | 80 81 99 | 80 82 103 | 80 82 103 | 80 82 103 |
| Catalyst content in the benzene, g/100mL | 0.6 | 1.0 | 1.5 | 2 | 3 | |
| Propylene conversion % | 86.7 | 90.2 | 99.2 | 99.9 | 100 | |
| Product isopropylbenzene selectivity % | 90.9 | 90.0 | 88.3 | 86.3 | 86.0 | |
Example 6～10
These example explanations this implementation of processes effect under the situation of different feeds benzene alkene ratio.
Adopt reactive distillation column and the catalyst identical, be in the charging rate of benzene that 5mL/min is constant, the ratio of normal pressure, backflow benzene and benzene feed is that catalyst content is the charging rate of change propylene under the condition of 2g/100mL in 6: 1, benzene with example 1～5.The result of the test of resulting different feeds benzene alkene ratio is listed in table 2.
Table 2
| Example | 6 | 7 | 8 | 9 | 10 | |
| Benzene feed alkene ratio | 1.25∶1 | 1.5∶1 | 1.75∶1 | 2∶1 | 3∶1 | |
| Reaction temperature ℃ | At the bottom of the tower of cat head middle part | 80 84 118 | 80 83 113 | 80 82 103 | 80 81 99 | 80 81 96 |
| Product is formed % | Benzene isopropylbenzene diisopropylbenzene (DIPB) tri-isopropyl benzene | 29.6 55.7 13.3 1.4 | 41.76 47.35 10.01 0.88 | 54.1 40.6 4.8 0.50 | 58.35 37.35 3.96 0.34 | 69.14 27.99 2.69 0.18 |
| Propylene conversion % isopropylbenzene selectivity % benzene conversion per pass % | ＞99 79.1 70.3 | ＞99 81.3 58.3 | ＞99 88.5 46.0 | ＞99 89.6 41.7 | ＞99 90.7 30.8 | |
Example 11～15
These example explanations this implementation of processes effect under the situation of the different capacities of returns of overhead benzene.
Adopting reactive distillation column and the catalyst identical with example 1～5, is that 2g/100mL, normal pressure, benzene feed alkene ratio are under 1.75: 1 the condition at catalyst concn, change tower still heating voltage.The result of the test of the different capacities of returns of resulting overhead benzene is listed in table 3.
Table 3
| Example | 11 | 12 | 13 | 14 | 15 | |
| Backflow benzene/ | 2∶1 | 3.5∶1 | 6∶1 | 10∶1 | 15∶1 | |
| Reaction temperature ℃ | At the bottom of the tower of cat head middle part | 80 82 101 | 80 82 102 | 80 82 103 | 80 82 104 | 80 82 104 |
| Product is formed % | Benzene isopropylbenzene diisopropylbenzene (DIPB) tri-isopropyl benzene | 54.24 32.07 13.21 0.48 | 53.23 36.32 10.05 0.4 | 54.1 40.6 4.8 0.50 | 48.32 48.12 3.31 0.25 | 52.71 45.07 2.11 0.11 |
| Propylene conversion % isopropylbenzene selectivity % | ＞99 75.32 | ＞99 77.1 | ＞99 88.5 | ＞99 93.1 | ＞99 95.2 | |
Comparative Examples
But this Comparative Examples illustrate this technology with catalyst and reaction raw materials through the ground stable operation of fine homogenizing operational procedure guarantee system long period.
In the reactive distillation column identical with example 1～5, at catalyst concn is that 2g/100mL, benzene charging rate are that 5mL/min, benzene alkene ratio are that the catalyst with desired ultrafine particle of this technology and granular size that prior art is required carries out benzene-propylene alkylation process stability test respectively under the condition of 165 volts of 2: 1, tower still heating voltage.
Result of the test shows: according to USP5,019,669 and USP5, requirement in 118,872 is a catalyst with H β, itself and benzene are made slurries directly to be squeezed in the tower, the particle diameter of making the slurries rear catalyst is 10～50 μ m, feeds the benzene that contains catalyst liquid flooding promptly took place in 5 hours, and process can't be proceeded at all; As to adopt phosphorus heteropoly tungstic acid be catalyst, and the particle diameter of making the slurries rear catalyst is 8～50 μ m, and situation makes moderate progress, but with the increase of the duration of runs, the tower internal drop increases gradually, and pressure drop is excessive during to the 7th day causes liquid flooding and process is stopped in running.
In contrast liquid flooding or stifled tower phenomenon then do not appear in bimestrial operation process all the time through the phosphorus heteropoly tungstic acid catalyzer behind the fine homogenizing (granularity is 0.5～1 μ m).
The time dependent table 4 that the results are shown in of tower internal drop.
Table 4
Claims (11)
1. catalytic distillation method, it is characterized in that solid catalyst and first kind of liquid reactions material are entered reactive distillation column by the top of conversion zone behind fine homogenizing, react with the second kind of reaction mass counter current contacting that enters from the conversion zone bottom, catalyst directly recycles after catalyst separator is separated with liquid product or regenerates.
2. in accordance with the method for claim 1, it is characterized in that being provided with distilling period, conversion zone and stripping section in the said reactive distillation column, settle column plate in each section or/and the distillation filler.
3. in accordance with the method for claim 1, it is characterized in that being provided with conversion zone and stripping section in the said reactive distillation column, settle column plate in each section or/and the distillation filler.
4. according to claim 2 or 3 described methods, it is characterized in that the theoretical cam curve that is provided with in said conversion zone, stripping section, the distilling period is respectively 1～30,1～20,0～10.
5. according to claim 2 or 3 described methods, it is characterized in that said distillation filler and catalyst particle size ratio should be greater than 1000, the voidage of filler should be greater than 70%.
6. in accordance with the method for claim 1, it is characterized in that said solid catalyst comprises solid acid catalyst and solid base catalyst, solid acid catalyst comprises cationic ion-exchange resin, molecular sieve, inorganic oxide, clay, heteropoly acid or its salt and solid super acid catalyst; Solid base catalyst comprises anion exchange resin, hydrotalcite.
7. in accordance with the method for claim 6, it is characterized in that said solid acid catalyst is heteropoly acid or its salt of load or not load.
8. according to claim 1, one of 6 and 7 described methods, it is characterized in that the solid catalyst granularity behind the fine homogenizing is 0.01～1 μ m.
9. in accordance with the method for claim 1, it is characterized in that said reaction condition is: tower is pressed and is normal pressure～30 atmospheric pressure, tower still temperature is 100～300 ℃, the conversion zone temperature is 85～250 ℃, tower top temperature is 80～200 ℃, the charge ratio of first kind of liquid reactants and second kind of reactant is 1: 0～1, the overhead reflux ratio be 1: 1 to infinite reflux.
10. in accordance with the method for claim 9, the charge ratio that it is characterized in that said first kind of liquid reactants and second kind of reactant is 1: 0.05～1.
11. it is characterized in that in accordance with the method for claim 9, the charge ratio of said first kind of liquid reactants and second kind of reactant is to be applicable to decomposition reaction, oligomerisation reaction at 1: 0 o'clock.
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| US8846986B2 (en) * | 2011-04-26 | 2014-09-30 | Celanese International Corporation | Water separation from crude alcohol product |
| CN108479100A (en) * | 2018-04-19 | 2018-09-04 | 福州大学 | The catalytic distillation device of lipase resolving chiral 1- benzyl carbinols and the method for producing chirality 1- benzyl carbinols |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051020A (en) * | 1975-10-30 | 1977-09-27 | Commonwealth Oil Refining Co. Inc. | Hydrocarbon conversion process for removing sulfur and nitrogen with passage of catalyst particles in a series of spaced beds |
| US4471154A (en) * | 1983-06-10 | 1984-09-11 | Chevron Research Company | Staged, fluidized-bed distillation-reactor and a process for using such reactor |
| US5019669A (en) * | 1989-03-10 | 1991-05-28 | Chemical Research & Licensing Company | Alkylation of organic aromatic compounds |
| US5118872A (en) * | 1989-03-10 | 1992-06-02 | Chemical Research & Licensing Company | Process for conducting heterogeneous chemical reactions |
-
1998
- 1998-06-25 CN CN98102726A patent/CN1071590C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051020A (en) * | 1975-10-30 | 1977-09-27 | Commonwealth Oil Refining Co. Inc. | Hydrocarbon conversion process for removing sulfur and nitrogen with passage of catalyst particles in a series of spaced beds |
| US4471154A (en) * | 1983-06-10 | 1984-09-11 | Chevron Research Company | Staged, fluidized-bed distillation-reactor and a process for using such reactor |
| US5019669A (en) * | 1989-03-10 | 1991-05-28 | Chemical Research & Licensing Company | Alkylation of organic aromatic compounds |
| US5118872A (en) * | 1989-03-10 | 1992-06-02 | Chemical Research & Licensing Company | Process for conducting heterogeneous chemical reactions |
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