CN1147453C - Catalytic process for preparing ethylbenzene from dry gas - Google Patents
Catalytic process for preparing ethylbenzene from dry gas Download PDFInfo
- Publication number
- CN1147453C CN1147453C CNB001319248A CN00131924A CN1147453C CN 1147453 C CN1147453 C CN 1147453C CN B001319248 A CNB001319248 A CN B001319248A CN 00131924 A CN00131924 A CN 00131924A CN 1147453 C CN1147453 C CN 1147453C
- Authority
- CN
- China
- Prior art keywords
- tower
- absorption
- liquid
- ethylbenzene
- reactor
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a technique for preparing ethylbenzene from ethylene and benzene, and particularly to provides a novel technique for preparing the ethylbenzene by catalyzing dry gas. The present invention adopts an absorbent for absorbing the ethylene in the dry gas firstly, and then obtained fulvene liquid enters a reactor for a liquid phase reaction; the reaction can be guaranteed to be carried out in a liquid phase, the catalyst does not contact a gas phase, so the life of the catalyst is guaranteed. The present invention overcomes the defects of the technological conditions of a catalytic distillation (absorption) bubbling bed, etc., such as the contact of the gas phase and the catalyst, multiple side reactions, easy occurrence of the activity reduction of the catalyst, short life, etc., and the prevent invention is also suitable for other three-phase reactions (gas, liquid and solid) with the requirement that a catalyst can not contact a gas phase.
Description
The present invention relates to ethene and benzene and produce the technology of ethylbenzene, a kind of novel process of catalysis drying gas system ethylbenzene is provided specifically.
Vinylbenzene is a kind of important chemical material, generally adopts the ethylbenzene dehydrogenation method to produce.All adopted pure ethylene and benzene reaction synthesizing ethyl benzene in the past, ethylbenzene cost height, uneconomical.Dry gas is the tail gas of urging cracking to produce, and the gas that generally all acts as a fuel is burnt, and utilization ratio is very low.And contain abundant ethene (volume ratio about 16%) in the dry gas, utilizing the ethene synthesizing ethyl benzene in the cheap dry gas is a very significant problem, it not only can make full use of existing dry gas resource, and can reduce the cost of ethylbenzene and styrene product greatly, whole petroleum chemical industry is had far reaching significance.
The technical process of the catalysis drying gas system ethylbenzene that adopts at present roughly is divided into two kinds.A kind of is to adopt catalytic distillation (absorption) technology, dry gas and fresh benzene enter catalytic distillation (absorption) tower by tower bottom and top respectively, catalytic distillation (absorption) tower adopt tray column or packing tower member with catalyst distribution in tower, benzene reacts while absorbing dry gas, unreacted tail gas is discharged by cat head, obtain the mixture of reaction product ethylbenzene and benzene at the bottom of the tower, carry out later separation again and obtain ethylbenzene product.
Another kind is to adopt the bubbling bed process, and catalyzer is immersed in the benzene fully, and dry gas by the buried catalyzer, generates ethylbenzene with catalyst reaction with the form of bubbling, and then carries out later separation and obtain ethylbenzene product.
Catalysis drying gas system ethylbenzene generally adopts beta-zeolite molecular sieve catalyst, finds that side reaction is more in above two kinds of technical process experiment, and the easy inactivation of catalyzer, life-span are shorter.Through repeatedly research, exploration discovery, it is the immediate cause that causes this result that catalyzer contacts with gas phase, and when dry gas contacted with catalyzer, the small molecules hydro carbons can enter side reactions such as polymerization takes place in the zeolite micropore, cause catalyst channels to stop up and inactivation makes catalyst life shorten.
Catalytic distillation (absorption) technology has transformation efficiency height, selectivity is good, catalyst levels is few advantage, does not contact with gas phase but this technology can not guarantee catalyzer, thereby can not guarantee life of catalyst.This is by the decision of the mechanism of catalytic distillation (absorption) technology.In catalytic distillation (absorption) technology, can adopt filler fixed-bed structure and tray column structure.Must adopt big filler specific liquid rate to reach the purpose of guard catalyst for the filler fixed-bed structure, it is not directly contacted with gas phase.But unsurmountable problem is arranged in this kind structure: 1, be subjected to the restriction of bed voidage, the filler specific liquid rate can not be too big, otherwise can cause the tower can't normal running; 2, gas phase always will be passed through bed, can not guarantee that catalyzer contacts gas phase anything but.Adopt the tray column structure can guarantee the catalyzer bubble in liquid phase, and gas phase is by catalyzer, but because liquid phase is carried the gas phase that gas phase and reaction heat generates liquid-phase vaporization secretly all might contact with catalyzer.Therefore catalytic distillation (absorption) technology can not guarantee catalyst life.
The bubbling bed process can make catalyzer steep fully in liquid phase, can play the purpose of guard catalyst to a certain extent.But absorb control because the reaction of catalysis drying gas system ethylbenzene belongs to, and the bubbling bed is very low for the efficient that absorbs, thereby has determined the shortcoming that its transformation efficiency is lower, selectivity is relatively poor, catalyst levels is big.Simultaneously, in this technology, gas phase still will be passed through beds, thereby can not guarantee that catalyzer does not contact with gas phase fully.As seen, the bubbling bed process can not guarantee catalyst life.
In sum, more than two kinds of catalysis drying gas process for preparing ethylbenzene drawback is all arranged, promptly can not guarantee life of catalyst.
The technology that the purpose of this invention is to provide a kind of new catalysis drying gas system ethylbenzene, its adopts absorption agent that the ethene in the dry gas is absorbed earlier, enters and carries out liquid phase reaction in the reactor.This technical process can guarantee to be reflected in the liquid phase to be carried out, and makes catalyzer not contact with gas phase fully, thereby has guaranteed life of catalyst.It has overcome, and gas phase contacts with catalyzer under the processing condition such as catalytic distillation (absorption), bubbling bed, and side reaction is many, and catalyzer is prone to active reduction, short drawback of life-span.
The present invention absorbs the technology of reaction more earlier, promptly earlier the ethene in the dry gas is absorbed with fresh benzene, ethylbenzene, together enters in the reactor and reacts, and technical process is described in detail as follows with reference to accompanying drawing:
Fig. 1～3rd, process flow sheet of the present invention.
As shown in Figure 1, the 1st, absorption tower, the 2nd, Analytic Tower, the 3rd, reactor, the 4th, stabilizer tower, the 5th, product separation tower, the 6th, fulvene liquid pump, the 7th, poor alkene liquid pump, the 8th, interchanger, the 9th, reboiler, the 10th, turbine, the 11st, absorption agent, the 12nd, dry gas, the 13rd, fulvene liquid, the 14th, reaction product, the 15th, poor alkene liquid, the 16th, circulating absorption solution, the 17th, product extraction liquid, the 18, the 19th, tail gas, the 20th, advance the benzene tail gas from absorption tower, the 21st, absorption liquid, the 22nd, ethylbenzene product, the 23rd, reaction raw materials benzene.
Dry gas (12) is divided into and is one or more strands ofly entered by bottom, absorption tower (1), benzene also is divided into as fresh absorbent (11) and circulation absorption agent (benzene) (16) and is one or more strands ofly entered by top, absorption tower (1), control absorption tower (1) temperature is at 20～100 ℃, pressure is 1.0～3.0MPa, and liquid phase absorbs the back with the ethene in the gas phase and discharged by the tower still in absorption tower (1); Tail gas is discharged by absorption tower (1) cat head, enters the benzene absorption tower, reclaims the benzene vapour of carrying secretly in the tail gas.The absorption liquid of being discharged by absorption tower (1) can enter Analytic Tower (2) and be heated to 50～110 ℃, parses section H
2, N
2, CH
4, C
2H
6Deng gas, enter reactor (3) then and carry out liquid phase reaction with benzene feedstock, also can directly enter reactor (3) and carry out liquid phase reaction with benzene feedstock.Fulvene liquid (13) is warming up to 120～260 ℃ and enters reactor (3) reaction after the pump pressurization.For making liquid phase in the process that heats up, not parse gas phase, need fulvene liquid (13) to be forced into 3.0～6.0MPa with pump.The reaction product (14) of being come out by reactor (3) enters stabilizer tower (4) with reactor (3) inlet feed heat exchange after be decompressed to 0.8～2.5MPa by turbine (10), and control stabilization tower (4) temperature makes reaction product (14) parse H at 20～100 ℃
2, N
2, CH
4, CO
2, C
2H
6Deng gas.The shaft work of turbine (10) output can be supplied with fulvene liquid pump (6).Gas phase by stabilizer tower (4) extraction enters the benzene absorption tower, reclaims the benzene vapour of carrying secretly in the tail gas.One enters product separation tower (5) as product extraction liquid (17) by the poor alkene liquid (15) of stabilizer tower (4) tower still extraction, separate obtaining product ethylbenzene (22) and absorption agent benzene (21), another strand returned absorption tower (1) by pump as circulating absorption solution (16) and recycled after heat exchange.
In the technology provided by the invention, absorption tower (1), stabilizer tower (4) can adopt packing tower or tray column, reactor (3) can adopt slurry bed reactor, fixed-bed reactor or other forms of reactor, said reactor (3) can adopt 1～10 parallel connection or serial operation, and said absorption agent can adopt benzene, ethylbenzene, propyl benzene or their mixture.
For flow process shown in Figure 1, absorption agent (11), dry gas (12) and circulating absorption solution (16) can adopt the multiply sectional feeding, adopt two reactors (3) parallel operation, as shown in Figure 2.
Also can adopt no Analytic Tower (2) flow process for flow process shown in Figure 1, adopt two reactors (3) serial operation, as shown in Figure 3.
The present invention carries out owing to reaction can be controlled in the pure liquid phase, so can guarantee life of catalyst; In addition because the absorption tower has higher efficient, ethene in the dry gas almost completely can be absorbed, ethene has very high transformation efficiency in reactor, so the conversion of ethylene of this technology very high (near 100%), has product ethylbenzene selectivity height, characteristics that catalyst levels is few.Portion of energy can recycle in this technology, has reduced energy consumption; It is simple also to have device structure, catalyst loading, regeneration, the simple advantage of replacing.
Catalysis drying gas process for preparing ethylbenzene provided by the invention has overcome that gas phase contacts with catalyzer under the processing condition such as catalytic distillation (absorption), bubbling bed, drawbacks such as side reaction is many, catalyzer is prone to active reduction, the life-span is short have the advantage that side reaction is few, transformation efficiency is high, catalyst life is long.
The present invention is suitable for other gas, liquid, solid phase reaction of avoiding catalyzer to contact with gas phase equally.
Characteristics of the present invention and positively effect can be embodied from following embodiment.
Embodiment:
In catalysis drying gas system ethylbenzene mode device, at first adopted catalytic distillation (absorption) technology.Catalytic distillation (absorption) tower specification is φ 50 * 6m, in adorn four sections catalyst structures, drafted two prescription cases and tested: (1) last three sections members are the filler fixed bed, next the section be plate-type component, adopt general catalytic distillation (absorption) technology, catalyzer is not absorbed the complete submergence of agent.(2) four sections are all adopted plate-type component, and catalyzer is absorbed the complete submergence of agent on the column plate, similar bubbling bed structure.
Find through experiment, in the two prescription cases, ethene initial conversion very high (reaching about 99%), but reducing always.It is very fast that conversion of ethylene reduces trend in the experiment of scheme one, just drops to about 80% about 20 days; It is relatively slow that the middle conversion of ethylene of scheme two reduces trend, dropped to about 85% about 35 days.After this taked the multiple measure of increase recycle benzene amount again, all can not guarantee catalyst activity and life-span, the ethene turnover ratio is settled out, visible catalytic distillation (absorption) or bubbling bed process are not suitable for catalysis drying gas system ethylbenzene process.
The contrast experiment has adopted the afterreaction technology that absorbs earlier of the present invention, promptly utilize former φ 50 * 6m catalytic distillation (absorption) tower, employing benzene is absorption agent, earlier the ethene in the dry gas is absorbed, then absorption liquid is entered fixed-bed reactor (the inside reactor catalyzer is fully by the benzene submergence), ethene that absorbs and benzene react in pure liquid phase, and reaction product removes H
2, N
2, CH
4, CO
2, C
2H
6Behind gas, a part is advanced the separation of product separation tower and is obtained ethylbenzene product and recycle benzene, and another part returns the absorption tower recycling as the circulation absorption agent.After adopting this technology, the ethene initial conversion is more than 99%, near transforming fully, and the catalyzer continuous operation after 60 days transformation efficiency still can stably remain on about 96%.
By above-mentioned contrast experiment as can be seen, the afterreaction technology that absorbs earlier provided by the invention can obviously prolong catalyst life, guarantee reaction conversion ratio, be a good catalysis drying gas process for preparing ethylbenzene.
Claims (7)
1. the technology of a catalysis drying gas system ethylbenzene, it comprises reactor (3), product separation tower (5), it is characterized in that it also comprises absorption tower (1), Analytic Tower (2), stabilizer tower (4), employing absorption agent (11) absorbs the ethene in the dry gas (12) in absorption tower (1) earlier, then through Analytic Tower (2), be heated to 50～110 ℃ and remove the fulvene liquid (13) that a part of light constituent obtains, fulvene liquid (13) enters reactor (3) and benzene feedstock reaction again, the poor alkene liquid of the tower still of reaction product (14) after stabilizer tower (4) removes light constituent (15), a part is returned absorption tower (1) as circulating absorption solution (16), another part enters product separation tower (5) as product extraction liquid (17), separates to obtain product (21) and absorption agent (22); The temperature range on said absorption tower (1) is controlled at 20～100 ℃, and pressure is 1.0～3.0Mpa; Said fulvene liquid (13) is heated to 120～260 ℃, is forced into 3.0～6.0Mpa and enters reactor (3); The temperature range of said stabilizer tower (4) is controlled at 20～100 ℃, and pressure is 0.8～2.5MPa; Said absorption agent (11) can adopt benzene, ethylbenzene, propyl benzene or their mixture.
2. according to the technology of the said catalysis drying gas system ethylbenzene of claim 1, it is characterized in that said dry gas (12) or absorption agent (11) can be that one enters absorption tower (1) from a certain position, also can be divided into multiply and enter absorption tower (1) by different positions.
3. according to the technology of the said catalysis drying gas system ethylbenzene of claim 1, it is characterized in that the absorption liquid that comes out in bottom, said absorption tower (1) also can directly advance reactor (3).
4. according to the technology of the said catalysis drying gas system ethylbenzene of claim 1, it is characterized in that the circulation absorption agent (16) after stabilizer tower (4) removes light constituent can be that one enters absorption tower (1) from a certain position, also can be divided into multiply and enter absorption tower (1) by different positions.
5. according to the technology of the said catalysis drying gas system ethylbenzene of claim 1, it is characterized in that said reactor (3) can adopt 1～10 parallel connection or serial operation.
6. according to the technology of the said catalysis drying gas system ethylbenzene of claim 1, it is characterized in that said absorption tower (1) or stabilizer tower (4) can adopt packing tower or tray column.
7. according to the technology of the said catalysis drying gas system ethylbenzene of claim 1, it is characterized in that said reactor (3) can adopt slurry bed reactor or fixed-bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001319248A CN1147453C (en) | 2000-10-21 | 2000-10-21 | Catalytic process for preparing ethylbenzene from dry gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001319248A CN1147453C (en) | 2000-10-21 | 2000-10-21 | Catalytic process for preparing ethylbenzene from dry gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1293178A CN1293178A (en) | 2001-05-02 |
| CN1147453C true CN1147453C (en) | 2004-04-28 |
Family
ID=4594860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001319248A Expired - Fee Related CN1147453C (en) | 2000-10-21 | 2000-10-21 | Catalytic process for preparing ethylbenzene from dry gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1147453C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315761C (en) * | 2004-12-23 | 2007-05-16 | 中国科学院大连化学物理研究所 | Method of preparing ethyl benzene by saparating ethene and benzene under dry gas of catalysis |
| CN101735025B (en) * | 2009-12-02 | 2013-11-06 | 中国科学院广州能源研究所 | Method and device for separating dimethyl ether from one-step synthesis dimethyl ether gas phase |
| CN103965009B (en) * | 2014-04-17 | 2015-09-30 | 陕西延长石油（集团）有限责任公司炼化公司 | The method of the hydrocarbonylation tail gas ethylbenzene after a kind of catalysis drying gas preparation of styrene |
| CN113024339A (en) * | 2021-01-15 | 2021-06-25 | 宁波科元精化股份有限公司 | Production process for reducing liquid carried in hydrocarbon tail gas of ethylbenzene device |
-
2000
- 2000-10-21 CN CNB001319248A patent/CN1147453C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1293178A (en) | 2001-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1139559C (en) | Method for producing essentially unbranched octenes and dodecenes by oligomerising unbranched butenes | |
| CN1907932B (en) | Method for preparing dimethyl ether from methanol | |
| CN102372585B (en) | The bed process of alkylating aromatic hydrocarbon p-Xylol | |
| Zhang et al. | Sulfonic acid resin-catalyzed addition of phenols, carboxylic acids, and water to olefins: Model reactions for catalytic upgrading of bio-oil | |
| JPS58157893A (en) | Conversion of methanol to gasoline with improved gasoline yield | |
| CN101570469B (en) | Method for continuously producing isobutyl alcohol through hydrogenation of methylacrolein | |
| CN100548944C (en) | A kind of zeolite catalysis and separation method that improves yield of preparing olefin by methyl alcohol dewatering | |
| CN1438296A (en) | Three-section lift-pipe catalytic cracking process | |
| EP2516359B1 (en) | Process for preparing ethylbenzene | |
| Anantapinitwatna et al. | Effect of water content in waste cooking oil on biodiesel production via ester-transesterification in a single reactive distillation | |
| CN1147453C (en) | Catalytic process for preparing ethylbenzene from dry gas | |
| RU2440189C1 (en) | Catalyst and method of producing high-octane gasoline with low content of benzene and durene | |
| CN102516036A (en) | Process method for preparing methyl tert-butyl ether by differential reaction rectification and equipment for same | |
| CN101322945B (en) | Method for preparing sulphur-containing condensate oil modifying catalyst and use | |
| CN102452900B (en) | Method for preparing ethylene glycol from ethylene | |
| CN101423454B (en) | Method for preparing tert-butanol by extraction of carbon 4 hydrocarbon containing isobutene | |
| CN102603486A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN111056901A (en) | Reaction system and reaction method for preparing aromatic hydrocarbon through catalytic conversion of methanol | |
| CN100432039C (en) | Method for protective preparation of acidic ion exchange resin catalyst for lower fatty acid ester | |
| CN1304917A (en) | Process for preparing tert-butanol from isobutylene by hydration | |
| CN102060644B (en) | Method for preparing olefin by dehydration of methanol | |
| CN109694306B (en) | Method for preparing dimethylbenzene by efficiently converting methanol | |
| CN100395220C (en) | Method for isomerization of light hydrocarbon | |
| CN113651664A (en) | Method for conversion of benzyl alcohol | |
| CN111056902A (en) | Reaction system for recycling byproduct oxide in methanol-to-aromatics process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |