CN1250494C - Technological process for catalyzing dry gas to prepare ethylbenzene - Google Patents
Technological process for catalyzing dry gas to prepare ethylbenzene Download PDFInfo
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- CN1250494C CN1250494C CN 200410021102 CN200410021102A CN1250494C CN 1250494 C CN1250494 C CN 1250494C CN 200410021102 CN200410021102 CN 200410021102 CN 200410021102 A CN200410021102 A CN 200410021102A CN 1250494 C CN1250494 C CN 1250494C
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- drying gas
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 291
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 57
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000010521 absorption reaction Methods 0.000 claims abstract description 50
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 46
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 claims abstract description 10
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 110
- 230000011218 segmentation Effects 0.000 claims description 31
- 238000006555 catalytic reaction Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 241000282326 Felis catus Species 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000006900 dealkylation reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 3
- 230000020169 heat generation Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 230000029936 alkylation Effects 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000002407 reforming Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000004821 distillation Methods 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 10
- 238000007600 charging Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 244000256297 Euphorbia tirucalli Species 0.000 description 1
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YFPBWJDUUHCRBT-UHFFFAOYSA-N ethylbenzene;hydrate Chemical compound O.CCC1=CC=CC=C1 YFPBWJDUUHCRBT-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 small molecules hydro carbons Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a technical process for catalyzing dry gas to prepare ethylbenzene, which has the advantages that pipelines are not corroded, the benzene recovery rate reaches above 99.5%, and the energy consumption of devices reaches the minimum level in China. The devices comprises a water washing tower, an alkylation reactor, a coarse separation tower, an absorption tower, a benzene tower, a toluene eliminating tower, an ethylbenzene tower, a poly-ethylbenzene eliminating tower, a diethylbenzene tower, a heat exchanger, a pump and a tank. The technical process comprises the steps that firstly, catalyzing dry gas is washed by the water washing tower to eliminate MDEA carried by the dry gas; then, the dry gas enters the alkylation reactor to react, a reaction product is heat exchanged by the heat exchanger and enters the coarse separation tower, and non-condensable gas is condensed and cooled to 5 to 20 DEG C on the top of the coarse separation tower and enters the absorption tower; and after bottom liquid of the coarse separation tower is pressurized by the pump, circulation benzene, toluene, ethylbenzene and propylbenzene are orderly separated from the bottom liquid which enters the benzene tower, the toluene eliminating tower, the diethylbenzene tower, the poly-ethylbenzene eliminating tower and the diethylbenzene tower, and inverse alkylation reaction products enter the benzene tower after heat exchange. The technical process is suitable for reforming the existing technical process for catalyzing dry gas to prepare ethylbenzene.
Description
Technical field:
The present invention relates to system ethylbenzene technical field in the petrochemical complex, exactly it is a kind of catalysis drying gas process for preparing ethylbenzene flow process.
Background technology:
Benzene is a kind of important Organic Chemicals, it is rare to be mainly used in production benzene second, market has driven the sustainable growth of ethylbenzene output to cinnamic thriving demand, and the new and more cheap approach of therefore, open up new source raw materials used in the ethylbenzene production, seeking ethylbenzene production has great importance.
Ethylbenzene is as the raw material of styrene monomer, and it 90% is made through alkylated reaction by benzene and high concentration ethylene.The source of ethylene raw is significant to the ethylbenzene industrial expansion, and whether it is related to the economic benefit of ethylbenzene industry and runs well.Especially in China, the crude oil heavy, the light oil rate is low, and the source of ethylene raw is subjected to the restriction of petroleum resources character.Therefore, make full use of existing various forms and different concns, especially low-concentration ethane, show necessary especially for the situation of alleviating China's ethylene raw anxiety.
Catalytic cracking is the important course of processing that the refinery heavy oil degree of depth transforms and increases economic efficiency, and also is the important source that contains the dry gas of low-concentration ethane.China has tens of cover catalytic cracking unit now, produces nearly 1,000,000 tons of dry gas per year.Contain 10%～20% ethene in the dry gas, great majority are still useed process furnace fuel as with other dry gas composition so far, and this is undoubtedly the very big waste to useful resources.If utilize the ethene in the dry gas to produce ethylbenzene, can not only enlarge the source of ethylene raw, part is alleviated China's ethene contradiction that supply falls short of demand for a long time, can also open up new way for the comprehensive utilization of oil refinery dry gas, obviously increases economic benefit of enterprises.
The rare general employing ethylbenzene dehydrogenation method of benzene second is produced.All adopted pure ethylene and benzene reaction synthesizing ethyl benzene in the past, ethylbenzene cost height, uneconomical.
Utilizing the ethene synthesizing ethyl benzene in the cheap dry gas is a very significant problem, and it not only can make full use of existing dry gas resource, and can reduce the cost of ethylbenzene and styrene product greatly, and 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 catalyst deactivation, life-span are shorter.Through repeatedly research, exploration discovery, it is the immediate cause that causes this consequence 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, catalytic amount is few advantage, but this technology can not avoid catalyzer to contact with gas phase, 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.Need 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.Unsurmountable problem is arranged in this 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, gas phase still will be passed through beds in this technology, thereby can not guarantee that catalyzer does not contact with gas phase fully.As seen, the bubbling bed process can not guarantee catalyst life.China Patent No.: 87105054 disclose the patent of invention that a kind of name is called " process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst thereof ", it is a kind of benzene alkylation with ethylene, particularly be applicable to the catalyzer that adopts the refinery exhaust (as catalytic cracked dry gas) contain low-concentration ethane to use for the benzene alkylation processes of reaction raw materials, it is by China Petroleum Chemicals Corporation, Dalian Inst of Chemicophysics, Chinese Academy of Sciences and Fushun Petrochemical Company co-applications.Mobil Oil Corporation once applied in China that a patent of invention patent No. was in 1993: 93112744.0, name is called the patent of invention of " production of ethylbenzene ", and it is in gas phase benzene to be carried out alkylated reaction by the catalyzer that contains ZSM--5 with second is rare.To separate with ethylbenzene product by the by product diethylbenzene of vapor phase alkylation, in liquid phase, carry out alkylated reaction with benzene then and shift, can adopt zeolite beta to make catalyzer with the more ethylbenzene of further generation.China Patent No.: 99124797 disclose the patent of invention that a kind of name is called " by the method and apparatus of benzene and oil refinery dry gas catalytic distillation process alkylation to prepare ethylbenzene ", Gu this processing method has comprised thick oil refinery dry gas is carried out pretreated step, makes benzene and ethene carry out gas-liquid-three-phase alkylated reaction and make mixture of reaction products carry out the step of fractionation by distillation simultaneously at a kind of solid catalysis dosage in a catalytic distillation tower simultaneously, catalyzer will satisfy to provisioning request with performance, configuration and the type of feed of distillation filler simultaneously.The raw material dry gas is unprocessed and directly enter reactor in the aforesaid method.China Patent No.: 00131924.8 discloses the patent of invention that a kind of name is called " technology of catalysis drying gas system ethylbenzene ", it adopts absorption agent that the ethene in the dry gas is absorbed earlier, the fulvene liquid that obtains enters and carries out liquid phase reaction in the reactor, can guarantee to be reflected in the liquid phase and carry out, make catalyzer not contact fully, thereby guaranteed life of catalyst with gas phase.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, catalyzer is prone to and drawback such as actively reduces, the life-span is short.
Petroleum Plant No.2, Fushun Petro-Chemical Co., the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Luoyang Petrochemical engineering corporation once developed catalytic cracked dry gas system ethylbenzene technology jointly, and built up a cover 3 * 10 in 1993 at second branch factory of oil
4T/a preparing ethylbenzene from dry gas device is once opened the vapour success.Through running in 10 years, every index all reached development goal, and third generation technology experiment device built up in 1999.
But at that time 3 * 10
4T/a preparing ethylbenzene from dry gas device is a cover industrial experiment device, and the device energy utilizes unreasonable.Original design conditions: catalysis drying gas does not need the refining alkylation reaction device that directly enters, because catalysis drying gas contains H
2S makes that reactor and corrosive pipeline are serious, even stops up reactor; Recycle benzene only through a heat exchange (with reaction product) then all by the heating of recycle benzene process furnace, reach vaporization until temperature of reaction, and reaction product also to be cooled to 40 ℃ and enters absorption system again, reheat to feeding temperature enters distillation system at last; The filling of alkylation reaction device catalyzer is divided into 5 sections, and energy consumption is up to 3,750,000 kilocalories/ton ethylbenzene.Luoyang Petrochemical engineering corporation was to Dalian Petrochemical Industry Company's design one cover 10 * 10 afterwards
4T/a preparing ethylbenzene from dry gas device, it is and styrene device is united, and device design energy consumption is 1,900,000 kilocalories/ton ethylbenzene, and actual production is several higher than this.
Summary of the invention:
The purpose of this invention is to provide a kind of catalysis drying gas process for preparing ethylbenzene flow process, adopted dry gas washing and absorption technique, the MDEA after the desulfurization is deviate from, reach protection equipment, reach protection equipment, pipeline is not corroded, guard catalyst is not poisoned simultaneously.Utilize low temperature absorption tail gas, the benzene rate of recovery is reached more than 99.5%.Plant energy consumption is domestic minimum level, is 980,000 kilocalories/ton ethylbenzene, and ethylbenzene product reaches national top grade product standard.
(1) raw material treating part
Technology in the past: adopt not sweet dry gas, long-time running pipeline, equipment corrosion are serious, and reacting system pressure falls excessive, reaches 0.3MPa when maximum.
The present invention: adopt sweet dry gas, alleviated pipeline, equipment corrosion, easily cause the hydrocarbonylation poisoning of catalyst, reduce reactive behavior, need to adopt washing process that MDEA is removed but sweet dry gas contains MDEA.
(2) reactive moieties
Technology in the past:
(1) the alkylation reaction device adopts five sections equivalent fillings, and dry gas divides three sections injections.
(2) the alkylation reaction thing is cooled to 40 ℃ and goes into the absorption tower.
(3) pyritous alkylation reaction thing is used for the heating and gasifying recycle benzene, and the recycle benzene process furnace is used to improve the recycle benzene temperature.
(4) dealkylation reaction device inlet material needs to heat with thermal barrier.
The present invention:
(1) the alkylation reaction device adopts four sections inequality fillings, also can equivalent load, and dry gas divides three sections injections.
(2) the alkylation reaction thing is cooled to and goes into the rough segmentation tower about 140 ℃.
(3) pyritous alkylation reaction thing is used for heating cycle benzene, dealkylation reaction device inlet material, the vaporization of recycle benzene is finished by the heating of benzene cat head oil gas, the recycle benzene process furnace is mainly used in and goes into operation and ethylene concentration uses when low, and the recycle benzene process furnace can be stopped when ethylene concentration is higher than 18% (body).
(4) dealkylation reaction device inlet material is heated to temperature of reaction with the alkylation reaction thing.
(3) absorption portion
Technology in the past:
(1) the alkylation reaction thing is cooled to 40 ℃ and carries out flash distillation, absorption.
(2) the alkylation reaction thing carries out twice flash distillation, absorption under different pressures.
(3) absorption agent circulation in a large number in system.
(4) remove non-condensable gases at stabilizer tower after rich absorbent and the heat exchange of alkylation reaction thing.
(5) establish reboiler at the bottom of the stabilizer tower, stabilizer tower substrate material is gone into the benzene tower.
The present invention:
(1) the alkylation reaction thing is cooled to and goes into the rough segmentation tower about 140 ℃, carries out vapor-liquid separation.
(2) the rough segmentation cat head is chilled to 40 ℃, and 40 ℃ of non-condensable gases continue to be chilled to 10 ℃, and 10 ℃ of non-condensable gases are gone into the absorption tower.
(3) absorption agent is a diethylbenzene, and rich absorbent is directly into the reverse alkylation jar, and goes into the dealkylation reaction device after recycle benzene is mixed, and absorption agent is not at system's internal recycle.
(4) dealkylation reaction device inlet material is heated to temperature of reaction with the alkylation reaction thing.
(5) the rough segmentation tower bottom is established reboiler, goes into the benzene tower after the heat exchange of rough segmentation bottoms material, and non-condensable gas is in the benzene removed overhead.
(4) product separation part
Technology in the past:
(1) each tower of product separation part adopts normal pressure to separate, and has only ethylbenzene tower that steam can take place.
(2) toluene is interrupted extraction from benzene tower side line, carries part benzene secretly.
(3) absorption agent is an ethylbenzene tower substrate material, and circulation in a large number in system, and specifications of equipment such as stabilizer tower, benzene tower, ethylbenzene tower are bigger.
(4) de multi-ethyl tower adopts decompression, and steam does not take place cat head.
The present invention:
(1) each tower of product separation part adopts each cat head of pressurization separation all steam can take place.
(2) non-condensable gas is extracted from the benzene cat head, and benzene tower side line goes out recycle benzene, and toluene is extracted out from the ethylbenzene cat head, and the ethylbenzene tower side line goes out ethylbenzene product.
(3) absorption agent is that diethylbenzene is the process material, and not at system's internal recycle, specifications of equipment such as rough segmentation tower, benzene tower, ethylbenzene tower are less, and it is less to be used for heating heat.
(4) de multi-ethyl tower adopts atmospheric operation, and steam can take place cat head, does not have pumped vacuum systems.
(5) between benzene tower and alkylation reaction device, form pressure reduction, to utilize benzene tower oil gas heating vaporization recycle benzene.
Advantage of the present invention is:
(1) in the existing technical process, the raw material dry gas is unprocessed and directly enter reactor, and is serious to equipment and corrosive pipeline; the present invention has adopted dry gas washing and absorption technique; MDEA after the desulfurization is deviate from, reach protection equipment, pipeline is not corroded, guard catalyst is not poisoned simultaneously.
(2) reaction product is rationally utilized heat energy through enter the rough segmentation tower after the heat exchange about 140 ℃, has promptly avoided after the reaction product cooling temperature-rise period again.
(3) the benzene pressure tower is improved, utilize cat head oil gas heat heating cycle benzene, it is reached to reaction conditions, significantly reduce the load of process furnace, thus energy efficient.
(4) utilize low temperature absorption tail gas, the benzene rate of recovery is reached more than 99.5%.
(5) the alkylation reaction device adopts four sections inequality fillings.
(6) plant energy consumption is domestic minimum level, is 980,000 kilocalories/ton ethylbenzene, and ethylbenzene product reaches national excellent superfine product standard.
Description of drawings:
Fig. 1 is a catalysis drying gas process for preparing ethylbenzene schematic flow sheet.
Fig. 2 is a catalysis drying gas process for preparing ethylbenzene schematic flow sheet.
1 is water wash column in the accompanying drawing, the 2nd, and dry gas divides flow container, and the 3rd, the alkylation reaction device, the 4th, recycle benzene process furnace, the 5th, recycle benzene surge tank, the 6th, reverse alkylation charging stock tank, the 7th, dealkylation reaction device, the 8th, rough segmentation tower, the 9th, absorption tower, the 10th, the benzene tower, the 11st, take off toluene tower, the 12nd, ethylbenzene tower, the 13rd, de multi-ethyl tower, the 14th, the diethylbenzene tower, (1) is fresh water, (2) are dry gas, (3) be fresh benzene, (4) be tail gas, (5) are the ethylbenzene tower chargings, and (6) are absorption agents, (7) be propyl benzene, (8) be high boiling material, (9) ethylbenzene, (10) are toluene.
Embodiment:
Characteristics of the present invention and positively effect can be embodied from following application example.
The present invention includes reactive moieties, absorption portion and product separation part, it is characterized in that: catalysis drying gas enters dry gas and divides flow container (2) Fen Silu to enter alkylation reaction device (3) reactant to enter rough segmentation tower (8) after heat exchange after MDEA is deviate from water wash column (1) washing, reverse alkylation material self-absorption tower (9) comes, with enter dealkylation reaction device (7) after benzene mixes and react, reaction product enters benzene tower (10) respectively with rough segmentation tower (8) substrate material after heat exchange.The alkylation reaction product enters rough segmentation tower (8) after a series of heat exchange are cooled to 100～150 ℃, cat head oil gas enters the rough segmentation return tank of top of the tower after the condenser portion condensation, phlegma is squeezed into the rough segmentation column overhead as backflow, non-condensable gas enters condenser and is chilled to 5～15 ℃ behind voltage-controlled valve, gas phase enters absorption tower (9), liquid phase is from flowing into rough segmentation column overhead return tank (integral type), rough segmentation bottoms material enters benzene tower (10) after the pump pressurization separates, the rough segmentation column overhead is condensed to 5～15 ℃ non-condensable gas and enters absorption tower (10) and top-down absorption agent ((6)) counter current contact, and wherein heavy constituent absorb.Tail gas is discharged from the absorption tower cat head, and a part is as fuel in the device, and remainder enters pipe network.Phlegma is as backflow, and non-condensable gas enters rough segmentation tower (8).Benzene is extracted out from benzene tower (10) side line, a part is sent into recycle benzene jar (5), another part is sent into reverse alkylation batch can (6), toluene is extracted out to enter from stripping section and is taken off toluene tower (11), benzene bottoms material enters ethylbenzene tower (12), topping ethylbenzene steams from cat head, a cooling back part is as refluxing, another part is as taking off toluene tower (11) charging, after taking off toluene tower (11) separation, toluene steams from piptonychia benzene column overhead, and a cooling back part is as backflow, another part is sent into the toluene jar, wherein toluene send can be continuously also can periodical operation, a part of ethylbenzene steams at the bottom of taking off toluene tower (11) tower, sends into the ethylbenzene jar after the cooling, most of ethylbenzene is extracted out from ethylbenzene tower (12) side line, and the ethylbenzene jar is sent into as product in the cooling back.The bottoms material enters de multi-ethyl tower (13) after pressurization, diethylbenzene, propyl benzene etc. steam from cat head, a part is as refluxing, another part is as diethylbenzene tower (14) charging, it at the bottom of the tower high boiling material, wherein but high boiling material is sent also periodical operation continuously, propyl benzene steams from diethylbenzene tower (14) cat head, a part is as refluxing, another part goes out device as product after cooling off, wherein propyl benzene send can be continuously also can periodical operation, be diethylbenzene at the bottom of the diethylbenzene tower, as absorption agent through heat exchange, be cooled to 20～50 ℃ and enter absorption tower (9).
1.1MPa, 40 ℃ catalysis drying gas enters the water wash column washing from system, washing water is that fresh water recycles (wherein having additional), emerges in most of MDEA in the gas, the dry gas MDEA concentration after the washing is reduced to below the 1ppm.
Dry gas after the washing enters and divides three the tunnel to enter the alkylation reaction device after dry gas divides flow container, and the tandem that flow and reaction bed temperature whenever all are housed is on the way regulated, so that each strand dry gas distributes in accordance with regulations.Be reflected at 0.95MPa, 410 ℃, benzene: ethene is to carry out under 5: 1 the condition.Reaction product is at 0.85MPa, 380 ℃ of warps and recycle benzene secondary heat exchange, reverse alkylation charging heat exchange, after the heat exchange of recycle benzene, at 0.7MPa, 235 ℃ and de-salted water heat exchange, the saturation steam of 0.3MPa takes place, at 0.65MPa, 187 ℃ with benzene tower charging heat exchange after with 0.6MPa, 140 ℃ enter the rough segmentation tower, the 1.4MPa that the self-absorption tower comes, 252 ℃ diethylbenzene enters the reverse alkylation batch can as the reverse alkylation material, 1.2MPa, 177 ℃ recycle benzene self-circulation benzene jar enters the reverse alkylation batch can, mix the back with the reverse alkylation material and be forced into 3.5MPa by the pump extraction, 185.4 ℃, carry out dealkylation reaction through ℃ entering the dealkylation reaction device with the heat exchange to 260 of alkylation reaction product, reaction conditions is 3.4MPa, 260 ℃, reaction product enters the benzene tower through voltage-controlled valve.
0.6MPa, alkylation reaction product and 1.3MPa, 40 ℃ of benzene cat head non-condensable gases of 140 ℃ enter the rough segmentation tower respectively.Cat head oil gas is at 0.55MPa, 106.5 ℃ being chilled to 39 ℃ through rough segmentation overhead condensation water cooler enters return tank of top of the tower, gas phase is chilled to 10 ℃ through the absorption tower feed cooler, gas phase enters the absorption tower, liquid phase enters return tank of top of the tower (integral type), backflow is extracted out after flow and the adjusting of return tank liquid level tandem by rough segmentation trim the top of column pump and is returned the rough segmentation cat head as backflow, the rough segmentation bottoms is extracted out at 1.5MPa by benzene tower fresh feed pump, 120 ℃ through with the heat exchange of alkylation reaction product after enter the benzene tower to 170 ℃, enter the non-condensable gas and the top-down absorption agent counter current contact on absorption tower, heavy constituent such as benzene are absorbed, tail gas self-absorption cat head is at 0.4MPa, 28.5 ℃ to system, liquid is at 0.45MPa at the bottom of the absorption tower, 17.4 ℃ through the reverse alkylation fresh feed pump add be pressed in 0.45MPa and absorption agent heat exchange after at 1.4MPa, 200 ℃ enter the reverse alkylation batch can.
The steam that steams from the benzene cat head is in 1.38MPa, 194 ℃ and recycle benzene heat exchange, make the recycle benzene gasification, at 187.5 ℃ the 0.3MPa saturation steam takes place again, condensation is cooled to 157 ℃ and enters benzene column overhead return tank, by benzene tower reflux pump extract out return to the benzene column overhead as backflow, gas phase in the benzene tower return tank is chilled to 40 ℃ through topping benzene water cooler and enters the rough segmentation tower, and phlegma flows into return tank.1.38MPa, 196.5 ℃ of recycle benzene extract out from benzene tower side line and enter the recycle benzene jar.The benzene bottoms enters ethylbenzene tower 1.45MPa, 277.5 ℃.
0.23MPa, 167.8 ℃ ethylbenzene overhead gas enters the ethylbenzene return tank of top of the tower through the 0.3MPa saturation steam takes place in 159.5 ℃, liquid phase is extracted out by the ethylbenzene tower reflux pump, a part is returned at the bottom of the ethylbenzene tower as backflow, another part is delivered to as topping ethylbenzene and is taken off toluene tower, and 169.3 ℃ ethylbenzene is extracted out from the ethylbenzene tower side line and send into the ethylbenzene product jar after being cooled to 40 ℃.The ethylbenzene tower substrate is posted the extraction of many ethylbenzene pump at 214.4 ℃ and is sent into de multi-ethyl tower.
0.23MPa, 132.3 ℃ piptonychia benzene overhead gas is chilled to 122 ℃ through piptonychia benzene overhead condensation water cooler and enters piptonychia benzene return tank of top of the tower liquid phase and extracted out by piptonychia benzene reflux pump, a part is returned as piptonychia benzene trim the top of column, another part is delivered to the toluene jar after being cooled to 40 ℃, ethylbenzene is extracted out by piptonychia benzene tower column bottoms pump at 171.2 ℃ at the bottom of the piptonychia benzene Tata, is cooled to 40 ℃ through the ethylbenzene water cooler and sends into the ethylbenzene product jar.
0.18MPa, 204.2 ℃ de multi-ethyl tower overhead gas is through taking place to enter the de multi-ethyl tower return tank in 194.4 ℃ behind the 1.0MPa saturation steam, liquid phase is extracted out through the de multi-ethyl tower reflux pump, a part is returned de multi-ethyl tower top as backflow, another part as the diethylbenzene tower charging send into the diethylbenzene tower.High boiling material at the bottom of the de multi-ethyl tower tower is extracted out by merchant's thing pump that boils at 236 ℃, is chilled to 40 ℃ through the high boiling material water cooler and sends into the high boiling material jar.
0.43MPa, 236.3 ℃ diethylbenzene column overhead gas enters diethylbenzene tower return tank through the 1.0MPa saturation steam takes place in 220.7 ℃, liquid phase is extracted out by diethylbenzene tower reflux pump, a part is returned the diethylbenzene tower as the diethylbenzene trim the top of column, and another part is chilled to 40 ℃ of carrying devices through the propyl benzene water cooler.Diethylbenzene Tata substrate is extracted out by the absorption agent pump 0.44MPa, 252 ℃ and is sent into the absorption tower as absorption agent.
The present invention is particularly suitable for transforming existing catalysis drying gas process for preparing ethylbenzene flow process.
Claims (11)
1, a kind of catalysis drying gas process for preparing ethylbenzene flow process, it comprises water wash column (1), alkylation reaction device (3), dealkylation reaction device (7), rough segmentation tower (8), absorption tower (9), benzene tower (10), take off toluene tower (11), ethylbenzene tower (12), de multi-ethyl tower (13), diethylbenzene tower (14), a series of interchanger, pump, jar, it is characterized in that: catalysis drying gas is at first washed through water wash column (1), deviate from the MDEA that carries in the dry gas, control MDEA content is below 1ppm, enter alkylation reaction device (3) reaction then, reaction product is through a series of interchanger heat exchange, enter rough segmentation tower (8), rough segmentation cat head non-condensable gases is cooled to 5-20 ℃ through condensation, enter absorption tower (9), liquid enters benzene tower (10) at the bottom of the rough segmentation tower after the pump pressurization, take off toluene tower (11), ethylbenzene tower (12), de multi-ethyl tower (13), diethylbenzene tower (14) order is isolated recycle benzene and is entered dealkylation reaction device (7) reaction together, and the dealkylation reaction product enters benzene tower (10) after heat exchange.
2, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1 is characterized in that: increase adsorption tower behind the dry gas water wash column.
3, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1, it is characterized in that: benzene tower (10) tower top temperature is controlled at 160-260 ℃, and pressure-controlling is at 0.5-2.0MPa; Utilize benzene tower (10) cat head oil gas heating cycle benzene, make its vaporization, utilize alkylation reaction product heating cycle benzene again, make its near or reach temperature of reaction.
4, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1, it is characterized in that: the alkylation reaction product enters the rough segmentation tower after a series of heat exchange, and the reaction product temperature is controlled at 100-150 ℃ and enters the rough segmentation tower.
5, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1 is characterized in that: ethylbenzene is extracted out from the side line of ethylbenzene tower as product.
6, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1, it is characterized in that: diethylbenzene directly enters dealkylation reaction as absorption agent.
7, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1 is characterized in that: the steam of the low potential temperature heat generation different grades of said a series of interchanger utilizations, and also with other low-temperature receiver heat exchange.
8, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1 is characterized in that: the filling of catalyzer can segmentation in the alkylation reaction device, adopts the inequality filling.
9, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1, it is characterized in that: said ethylbenzene tower, de multi-ethyl tower, diethylbenzene tower, they are operated in the 0.1-0.6MPa scope, according to the temperature of cat head oil gas 0.3MPa or 1.0MPa saturation steam can take place.
10, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 1 is characterized in that: the propyl benzene of sending from the diethylbenzene reflux pump to carry out heat exchange with low-temperature receiver or other low-temperature receivers of this device according to what of heat.
11, a kind of catalysis drying gas process for preparing ethylbenzene flow process according to claim 5 is characterized in that: the ethylbenzene of extracting out from the ethylbenzene tower side line to carry out heat exchange with low-temperature receiver or other low-temperature receivers of this device according to what of heat.
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| CN 200410021102 CN1250494C (en) | 2004-02-02 | 2004-02-02 | Technological process for catalyzing dry gas to prepare ethylbenzene |
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| CN 200410021102 CN1250494C (en) | 2004-02-02 | 2004-02-02 | Technological process for catalyzing dry gas to prepare ethylbenzene |
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| CN104045499B (en) * | 2013-03-12 | 2016-09-14 | 中石化洛阳工程有限公司 | A kind of utilize the method for ethylene production aromatic hydrocarbons in oil refinery dry gas |
| CN104341264B (en) * | 2013-08-08 | 2018-02-16 | 中石化洛阳工程有限公司 | A kind of vapor phase method contains ethene and/or propylene gas system ethylbenzene and/or propyl benzene product separating technique |
| CN104860790B (en) * | 2015-05-26 | 2016-08-24 | 天津大学 | Utilize the device and method of the ethylbenzene manufactured from ethylene that oil refinery dry gas pressure-variable adsorption reclaims |
| CN106278797B (en) * | 2015-06-12 | 2018-11-20 | 中国石油化工股份有限公司 | The method of catalysis drying gas production ethylbenzene |
| CN106588557B (en) * | 2017-01-13 | 2019-04-19 | 山东京博石油化工有限公司 | A kind of method that oil refinery dry gas prepares ethylbenzene |
| CN107603669B (en) * | 2017-10-26 | 2019-08-27 | 中国石油化工股份有限公司 | The ethylene recovery system of catalytic cracked dry gas |
| CN107935805B (en) * | 2017-12-15 | 2020-08-25 | 大连理工大学 | Production expansion method of device for preparing ethylbenzene from dry gas based on raw material ethylene content increase |
| CN108299142A (en) * | 2017-12-25 | 2018-07-20 | 中国石油集团东北炼化工程有限公司沈阳分公司 | A kind of energy-saving method of catalysis drying gas ethylbenzene |
| CN109351289A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A method of control alkylation reactor bed temperature rise |
| CN109351288A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A kind of technique controlling the temperature rise of alkylation reactor bed |
| CN110776391B (en) * | 2019-11-11 | 2022-05-31 | 山东京博石油化工有限公司 | Device and method for preparing ethylbenzene from dry gas |
| CN112028732A (en) * | 2020-05-13 | 2020-12-04 | 宁波科元精化股份有限公司 | Method for reducing non-aromatic hydrocarbon at side line of benzene tower |
| CN112321379B (en) * | 2020-10-22 | 2023-05-09 | 北京惠尔三吉绿色化学科技有限公司 | Energy-saving and environment-friendly method for preparing ethylbenzene from dry gas |
| CN113480395B (en) * | 2021-07-02 | 2022-07-08 | 大连理工大学 | Flash separation process and device for preparing ethylbenzene from ethylene-rich gas |
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