CN1041693C - Catalytic rectifying tower and its usage - Google Patents
Catalytic rectifying tower and its usage Download PDFInfo
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- CN1041693C CN1041693C CN 91106585 CN91106585A CN1041693C CN 1041693 C CN1041693 C CN 1041693C CN 91106585 CN91106585 CN 91106585 CN 91106585 A CN91106585 A CN 91106585A CN 1041693 C CN1041693 C CN 1041693C
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- catalytic
- rectifying tower
- rectification process
- catalytic reaction
- reaction rectification
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Abstract
The present invention relates to a catalytic reaction rectifying tower and the service application thereof. Tower tray filling material of the catalytic reaction rectifying tower of the present invention is prepared from active material containing catalysts. The present invention basically solves the problems of packing and filling catalysts of the present catalytic reaction rectifying tower, pressure drop caused by loading the catalysts and unbalanced catalytic reaction and rectification operation. The catalytic reaction rectifying tower of the present invention is suitable for rectifying processes such as esterification, ester interchange, sponification, hydrolysis, hydration, alkylation, dissimilation, halogenation, amination, acetylation, nitration, dehydration, oxidation, etherification, etc.
Description
The present invention is a kind of catalytic rectifying tower and uses thereof, and it belongs to the organic compound catalytic reaction and separates, and it is made up of tower body, column plate and catalyst.
Usually, in Chemical Manufacture, reacting with the operation that separates two lists is to finish in the independent equipment of two classes; Course of reaction is carried out in various forms of reactors, and unreacted reactant, product and accessory substance are then separated in separation equipment.In order to improve product is yield, reduces the investment and the energy consumption of equipment, develop a kind of will react and equipment that separation process combines is that people are striving for always.Wherein, catalytic rectifying tower is exactly the special equipment that is applicable to the distillation process of chemical reaction.Owing in catalytic rectifying tower, can finish catalytic reaction simultaneously and separate two processes with rectifying, simplified flow process, reduced equipment investment; Because reactant and the timely of product separate, and have destroyed chemical balance, reaction is tending towards fully, improved the conversion ratio and the selectivity of reaction; Because product can steam from reaction zone at any time, improve concentration of reactants, thereby increased reaction speed, improved production capacity; For exothermic reaction since reaction heat absorbed by material vaporization, thereby saved heat energy and saved heat-obtaining equipment; Simultaneously in an equipment, obtained purer product.Therefore the development of catalysis reaction rectifying device more and more is subjected to the attention of domestic and international chemist.At US3, a kind of catalytic distillation device is disclosed in 634,534, its purpose is that catalyst is contained in the rectifying column, realizes that catalytic reaction and distillation operation carry out simultaneously.Its formation is the downspout that catalyst is placed board-like tower tray, as a fixed bed.Its weak point is the restriction that is subjected to the rectifying technical process because of the size of downspout, so that the loadings of catalyst seldom, has influenced entire reaction rectifying output of column.At US4, in 215,011, revealed a kind of from C
4The antigravity system of isobutylene separation in heating up in a steamer.Its purpose is with the catalyst catalytic tower of packing into, makes catalyst layer leave a fixed gap again, reduces resistance.Its content is that catalyst is wrapped in the parcel made from glass wool cloth, adds stainless (steel) wire, places on the gripper shoe, leaves the space between the parcel, makes vapour-liquid two convection current of being on good terms pass reaction bed.Its weak point is a complex structure, the cost height, and the filling and draw off all pretty troublesome, diffusion process is obstructed, reaction speed discloses a kind of catalytic distillation novel device and antigravity system slowly in CN application number 8810905.5, its purpose is that catalyst need not any special packing, and in the beds of the conversion zone of directly packing into, thereby simplifies the filling operation of catalyst.Its content is catalyst directly to be loose to open supporting on the column plate, and every section bed is equivalent to a fixed bed, and the column plate of fractionation is housed between the bed.Though being logistics, its shortcoming can directly contact with catalyst, but can not really play reaction and fractionation and be both the effect of carrying out, because liquid and vapor capacity can not contact in beds in convection current, in fact fractional distillation process is to carry out on the column plate between the bed, in addition, in gas channel, can not react, also do not play fractionation, that has reduced equipment effectively utilizes the space.It seems that more than making a kind of is desirable in perfect catalytic rectifying tower to the greatest extent.
The objective of the invention is to avoid above-mentioned weak point of the prior art and provide a kind of catalyst without any need for packing, type of feed is just the same with the conventional rectification tower, filling quantity can be by the design of catalytic reaction output of column nonfertilization heat up in a steamer appointed condition restriction, enough voidages are arranged, the mass-and heat-transfer effect, column plate that are similar to general rectifying column both catalyst carrier be the rectifying separation tray.Can satisfy the desirable catalytic rectifying tower that catalytic reaction requires can satisfy again the distillation operation condition.
Purpose of the present invention can reach by following measure: the part or all of column plate of catalytic rectifying tower mixes back machine-shaping by catalytically-active materials, reinforcing material, pore-foaming agent, adhesive, auxiliary agent.Can adopt conventional form, compression molding, cutting spicing forming type or the like, for moulding needs to adopt rivet welding, lead, cutting, machining process such as bonding; Can activate reshaping earlier also can first moulding reactivation.
Purpose of the present invention can also reach by following measure:
Catalytic rectifying tower of the present invention can be a packed tower, also can be plate column, bubble column, float and cut down tower or its any combination.
Wherein be used for dumped packing or corrugated plate shape such as the Raschig ring, Bao Erhuan, Wheel ring packing, rectangular saddle ring of packed tower, spherical, column, cellular structured packing can be with containing activity of such catalysts materials processing moulding.The sieve plate of same plate column, corrugated plating, bubble cap plate, the floating column plate that cuts down also can be with the materials processing moulding alive that contains catalyst.
The Tata plate of catalytic reaction rectification of the present invention can be all with the column plate that contains activity of such catalysts materials processing moulding.For those technical process higher to separation requirement, also can be on the catalytic reaction column plate or below set up the common column plate that only plays centrifugation.
Catalytic rectifying tower of the present invention is used for the distillation process with catalytic reaction.
Concrete reaction with the catalytic reaction rectification process comprises esterification, ester exchange reaction, saponification, hydrolysis, hydration reaction, alkylated reaction, isomerization reaction, halogenation, saddle reaction, different acylation reaction, nitration reaction, dehydration, oxidation reaction, etherification reaction etc.Wherein the example of esterification is that maleic anhydride and ethanol synthesis generate diethyl maleate; The esterification of acetic acid and ethanol, propyl alcohol, butanols, ethylene glycol; Acrylic acid and ethyl esterification reaction; Boric acid and methanol esterification reaction.
The representative instance of ester exchange reaction is butyl acetate and ethanol synthesis; Rutgers and glycol reaction.
The example of saponification is that the dichlorohydrin saponification generates epoxychloropropane; The chloropropyl alcohol saponification generates expoxy propane; The methyl formate saponification generates formic acid.
The example of hydrolysis is that the acetic anhydride hydrolysis generates acetic acid; The rectifying of formaldehyde and hydrate thereof.
The example of hydration reaction is catalytic cracking C
4The isobutene in the hydrocarbon and the synthetic tert-butyl alcohol of water reaction.
The example of alkylated reaction is with ethene and the synthetic ethylo benzene of benzene reaction; The mixture that is used for benzene or 2-methyl-2-phenylpropane compartment dimethylbenzene and paraxylene.
The example of isomerization reaction is that the methylallyl isomery becomes-dimethyl chloride ethene.
The example of halogenation is that benzene and nitric acid are made nitrobenzene.
The example of dehydration is that the dehydration of tert-butyl alcohol catalysis flower generates isobutanol; The trimethyl carbinol dehydration generates isobutene.
The example of etherification reaction is catalytic cracking C
4Isobutene in the hydrocarbon and methyl alcohol reaction synthesize methyl tert-butyl ether; Catalytic cracking C
52-methyl butene in the cut and methyl alcohol reaction generate tert amyl methyl ether(TAME).
The drawing of accompanying drawing is described as follows:
Fig. 1:
(I) rectifying section, (II) conversion zone, (III) stripping section, (1) feed line, (2) liquid re-distributor, (3) pipeline, (4) condenser, (5) pipeline, (6) return tank
(7) pipeline
(8) pipeline
(9) pipeline
(10) reboiler
(11) pipeline
(12) pipeline
(13) catalyst column plate
The present invention is described in further detail below in conjunction with (accompanying drawing) embodiment.
Catalytic cracking C
4Isobutene in the hydrocarbon and methyl alcohol reaction synthesize methyl tert-butyl ether (MTBE).
The catalytic cracking C that contains isobutene 5%～80%
4The mixed according to a certain ratio material of hydrocarbon and methyl alcohol enters the catalytic rectifying tower that 10 * 10 * 3 Raschig ring cationic ion-exchange resin filler is housed through pipeline (1), at conversion zone (I) reaction pressure 0.6～1.0MPa, under 40～100 ℃ of conditions of reaction temperature, after continuously carrying out reactive distillation processes, unreacted C
4The hydrocarbon vapour phase rises and to enter rectifying section (II) and phegma counter current contacting through repeatedly caloic exchange, after making overhead product reach separation requirement, enter condenser (4) condensation but after pipeline (5) enters return tank (6) through tower top outlet pipeline (3), the liquid C in the return tank
4, a part is back to cat head through pipeline (7) and from top to bottom enters conversion zone (II) through liquid re-distributor (2) and participate in reactive distillation again, and another part goes out device through pipeline (8).The product MTBE that reaction generates enters tower reboiler (10) through stripping section (III), and vaporization is after pipeline (11) returns at the bottom of the tower, and tower bottom product MBE goes out device through pipeline (12).Conversion for isobutene 90%～99.5%.
Embodiment 2
Catalytic cracking C
4The isobutene in the hydrocarbon and the synthetic tert-butyl alcohol (TBA) of water reaction.
With acetic acid cationic ion-exchange resin and reinforcing material, pore-foaming agent, adhesive, process the regular column plate of corrugated plating after other auxiliary agents mix and dress up catalytic rectifying tower; The spent glycol monomethyl ether is as reaction dissolvent, and flow process is with embodiment 1.
Conversion zone temperature ℃ 40～100
Volume space velocity h
-11～5
Isobutene conversion % 90～95
Maleic anhydride and ethanol synthesis generate diethyl maleate.
Solid acid catalyst is processed into bubble cap plate dresses up catalytic rectifying tower.Operate under normal pressure, flow process is with embodiment 1.
Conversion zone temperature ℃ 50～115
Volume space velocity h
-10.5～4
Alkyd M mol 2～6
Cis-butenedioic anhydride conversion ratio % 90～99.3
The alkylated reaction of ethene and the synthetic ethylo benzene of benzene reaction.
Molecular sieve catalyst is processed into floating cut down column plate and dress up catalytic rectifying tower.Flow process is with embodiment 1.
Reaction temperature ℃ 110～250
Benzene alkene is than mol 4～8
Liquid phase volume air speed h
-13～8
Conversion of ethylene % 95～98
Ethylo benzene selectivity % 80～86
Total reflux operation, ethylene gas enters from the conversion zone bottom.
Tert-butyl alcohol catalytic dehydration generates isobutene.
Cation exchange resin catalyst is processed into the structured packing of wheel shape dresses up catalytic rectifying tower.Flow process is with embodiment 1.
Reaction temperature ℃ 45～100
Volume space velocity h
-11～5
Tert-butyl alcohol conversion ratio % 90～99
Isobutene purity % 95～99.9
Catalytic cracking C
52-methyl butene in the cut and methyl alcohol reaction generate tert amyl methyl ether(TAME).
Macropore sulfonic acid ion-exchange resin is processed into the corrugated plate shape structured packing, dresses up catalytic rectifying tower.Flow process is with embodiment 1.
Reaction temperature ℃ 40～100
Reaction pressure MPa 0.5～1
Alfin ratio 0.6～1.1
Volume space velocity h
-11～8
Total conversion % 〉=91.2 of 2-methyl butene
The present invention compares present technology and has following advantage
1, realized that catalytic reaction and distillation process carry out synchronously.
2, the requirement that vapour-liquid two relative currents pass is satisfied in catalyst column plate space.
3, removed the worry of the packing of catalyst, filling in the catalytic distillation.
4, bed temperature be evenly distributed, constant, improved conversion ratio, prolonged catalyst Life-span.
5, of many uses, all can use the distillation process with catalytic reaction. To string is arranged The course of reaction of connection side reaction also can be used.
Claims (19)
1, a kind of catalytic rectifying tower is made up of tower body, column plate and catalyst, it is characterized in that part or all of column plate is by containing activity of such catalysts material reinforcing material, pore-foaming agent, adhesive, auxiliary agent mixing back machine-shaping.
2,, it is characterized in that it being packed tower, plate column, bubble column, float and cut down tower or its any combination according to the described catalytic rectifying tower of claim 1.
3,, it is characterized in that column plate is dumped packings such as the Raschig ring that is used for packed tower, Bao Erhuan, wheel shape, rectangular saddle ring, spherical, column or corrugated plate shape, cellular structured packing according to the described catalytic rectifying tower of claim 1.
4,, it is characterized in that column plate is sieve plate, corrugated plating, bubble cap plate, the floating column plate that cuts down according to the described catalytic rectifying tower of claim 1.
5,, it is characterized in that whole column plates all are with containing activity of such catalysts materials processing moulding according to the described catalytic rectifying tower of claim 1.
6, according to the described catalytic rectifying tower of claim 1, it is characterized in that be on contain the column plate of catalyst reactive material or below set up the common column plate that only plays centrifugation.
7; a kind of purposes of catalytic rectifying tower; it is characterized in that being used for the catalyzing esterification reactive distillation processes; ester exchange catalytic reaction rectification process; saponification catalytic reaction rectification process; the hydrolysis catalysis reaction distillation process; hydration catalytic reaction rectification process; alkyl catalytic reaction rectification process; isomerization catalytic reaction rectification process, halogenation catalytic reaction rectification process; amination catalytic reaction rectification process; acetylation catalytic reaction rectification process; nitrated catalytic reaction rectification process; the catalytic dehydration reactive distillation processes; the oxidation catalysis reactive distillation processes; etherificate catalytic reaction rectification process.
8, kind require the purposes of 7 catalytic rectifying tower according to power, it is characterized in that described catalyzing esterification reactive distillation processes is maleic anhydride and ethanol; Acetic acid and ethanol, propyl alcohol, butanols, ethylene glycol; Acrylic acid and ethanol; Boric acid and methyl alcohol are by the catalyzing esterification reactive distillation processes.
9, according to the purposes of the catalytic rectifying tower of claim 7, it is characterized in that described ester exchange catalytic reaction rectification process is butyl acetate and ethanol; Rutgers and glycol ester exchange catalytic reaction rectification process.
10,, it is characterized in that described saponification catalytic reaction rectification process is that the dichlorohydrin saponification generates epoxychloropropane according to the purposes of the catalytic rectifying tower of claim 7; The chloropropyl alcohol saponification generates chloropropane; The methyl formate saponification generates formic acid by saponification catalytic reaction rectification process.
11,, it is characterized in that described hydrolysis catalysis reaction distillation process is that the aceticanhydride acid hydrolysis generates acetic acid according to the purposes of the catalytic rectifying tower of claim 7; The hydrolysis catalysis reaction distillation process of formaldehyde and hydrate.
12, according to the purposes of the catalytic rectifying tower of claim 7, it is characterized in that the described hydration catalytic reaction process of heating up in a steamer is catalytic cracking C
4The hydration reaction distillation process of the isobutene in the hydrocarbon and the synthetic tert-butyl alcohol of water reaction.
13,, it is characterized in that the synthetic ethylo benzene of described alkylation catalytic rectifying tower process ethene and benzene reaction according to the purposes of the catalytic rectifying tower of claim 7; Alkylation catalytic reaction rectification process with the mixture of butylbenzene 2-methyl-2-phenylpropane compartment dimethylbenzene and paraxylene.
14, according to the purposes of the catalytic rectifying tower of claim 7, it is characterized in that described isomerization catalytic reaction rectification process is that β methylallyl isomery becomes β, β--the isomerization catalytic reaction rectification process of dimethyl chloride ethene.
15,, it is characterized in that described halogenation catalytic reaction rectification process is the halogenation catalytic reaction rectification process that sodium bromide and sulphur and ethanol synthesis generate bromoethane according to the purposes of the catalytic rectifying tower of claim 7.
16, according to the purposes of the catalytic rectifying tower of claim 7, it is characterized in that described acetyl catalytic reaction rectification process is the acetylation catalytic reaction rectification process of aniline.
17,, it is characterized in that described nitrated catalytic reaction rectification process is with the nitrated catalytic reaction rectification process of benzene with nitric acid manufacturing nitrobenzene according to the purposes of the catalytic rectifying tower of claim 7.
18,, it is characterized in that described catalytic dehydration reactive distillation processes is that tert-butyl alcohol catalytic dehydration generates isobutene according to the purposes of the catalytic rectifying tower of claim 7; The trimethyl carbinol dehydration generates the catalytic dehydration reactive distillation processes of isobutene.
19, according to the purposes of the catalytic rectifying tower of claim 7, it is characterized in that described etherificate catalytic reaction rectification process is catalytic cracking C
4Isobutene in the hydrocarbon and methyl alcohol reaction synthesize methyl tert-butyl ether; Catalytic cracking C
52～methyl butene in the cut and methyl alcohol reaction generate the etherificate catalytic reaction rectification process of tert amyl methyl ether(TAME).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106585 CN1041693C (en) | 1991-10-15 | 1991-10-15 | Catalytic rectifying tower and its usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106585 CN1041693C (en) | 1991-10-15 | 1991-10-15 | Catalytic rectifying tower and its usage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1060228A CN1060228A (en) | 1992-04-15 |
| CN1041693C true CN1041693C (en) | 1999-01-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106585 Expired - Fee Related CN1041693C (en) | 1991-10-15 | 1991-10-15 | Catalytic rectifying tower and its usage |
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| Country | Link |
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| CN (1) | CN1041693C (en) |
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1991
- 1991-10-15 CN CN 91106585 patent/CN1041693C/en not_active Expired - Fee Related
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| CN1060228A (en) | 1992-04-15 |
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