CN100363315C - Method for synthesizing cumin from refinery propene - Google Patents
Method for synthesizing cumin from refinery propene Download PDFInfo
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- CN100363315C CN100363315C CNB2003101034365A CN200310103436A CN100363315C CN 100363315 C CN100363315 C CN 100363315C CN B2003101034365 A CNB2003101034365 A CN B2003101034365A CN 200310103436 A CN200310103436 A CN 200310103436A CN 100363315 C CN100363315 C CN 100363315C
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- propylene
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- benzene
- alkylation
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- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 241000510672 Cuminum Species 0.000 title 1
- 235000007129 Cuminum cyminum Nutrition 0.000 title 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 109
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 72
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 42
- 230000029936 alkylation Effects 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 48
- -1 hydrogen alkynes Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 31
- 239000007787 solid Substances 0.000 abstract description 12
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 10
- 230000002779 inactivation Effects 0.000 abstract description 7
- 230000009849 deactivation Effects 0.000 abstract description 6
- 239000012071 phase Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 150000001993 dienes Chemical class 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 238000002407 reforming Methods 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000006866 deterioration Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 3
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 3
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 241000282346 Meles meles Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for synthesizing cumene from propylene of refineries, which belongs to a method for synthesizing the cumene from benzene and propylene through alkylation reaction. The method of the present invention has the steps that first, propylene raw materials of the refineries enter a hydrogenation reaction vessel for selective hydrogenation reaction to eliminate alkyne and alkadiene in the propylene raw materials; then, after being purified and pretreated, the propylene raw materials of the refineries enter an alkylation reaction vessel to carry out alkylation reaction with the benzene under the action of catalysts to generate the cumene. The method of the present invention completely solves the problems of fast alkylation reaction catalyst deactivation, short regeneration period, etc. in the prior art by using propylene of the refineries as raw materials. The present invention has the advantages of further enhancement of the stability of the alkylation catalysts, difficult inactivation of the alkylation catalysts, long regeneration period, long total service life, stable device operation and high operation stability. When used for reforming the existing liquid-phase method technology and three-phase (gas, liquid and solid) method technology, the present invention has the advantages of low investment and fast effect taking.
Description
Technical field
The present invention relates to a kind of alkylating method, specifically, relate to a kind of method of synthesizing iso-propylbenzene.
Background technology
Isopropyl benzene is a kind of important Organic Chemicals, is mainly used in to produce phenol and acetone.At present, the method for synthesizing iso-propylbenzene has a variety of, and mainly to adopt with the molecular sieve be catalyzer, by benzene and the propylene method through the alkylation synthesizing iso-propylbenzene.Press the phase of alkylated reaction, synthesizing iso-propylbenzene technology can be divided into vapor phase process, liquid phase method, gas-liquid-solid three-phase method; Press the type of alkylation reactor, can be divided into technologies such as fixed bed, catalytic distillation tower, suspension bed.Wherein the liquid phase method fixed-bed process is the more a kind of method of present industrial employing.
Liquid phase method keeps raw material propylene all to be in liquid phase in charging and reaction process, working pressure is higher, be 2.5～3.5MPa, temperature is relatively low, be 120～170 ℃, its representative processes has UOP technology, Mobil/Badger technology, Dow/Kellog technology, EniChem technology and swallow metallization processes etc.These technologies all adopt fixed-bed reactor.
Raw material propylene can have two kinds, promptly separate polymerization-grade propylene (hereinafter to be referred as the cracking propylene) that makes and the propylene (hereinafter to be referred as crude propylene) that makes by the fractionation of refinery catalytic cracking gas by the lighter hydrocarbons cracking, at present industrial most of devices adopt the cracking propylene as raw material, and exist very problem such as fast inactivation of catalyzer when being raw material with the crude propylene all the time.
Uop Inc. has succeeded in developing Q-Max isopropyl benzene production technique the beginning of the nineties, uses the zeolite catalyst of the trade mark as MgAPSO-31, to substitute the said firm's solid phosphoric acid catalyst of exploitation in the past.It is reported that this catalyst stability is good, the regeneration period reaches 18 months, and regenerability is good, and entire life was above 5 years.According to Uop Inc.'s introduction, the MgAPSO-31 zeolite catalyst was used in 1996 former solid phosphoric acid method technological transformation, and investment and process cost are lower, good product quality, purity can reach 99.95%, and impurity such as n-proplbenzene and butylbenzene and bromine index are all low than solid phosphoric acid method in the product.This technology is at existing two covering devices of the U.S., and the overall throughput of its isopropyl benzene is 311kt/a; At existing two covering devices of China, throughput is 100kt/a.From domestic production device real-world operation situation, when adopting crude propylene to make raw material, the very fast inactivation of this catalyzer, its regeneration period has had a strong impact on the ordinary production of factory less than half a year.Therefore, with the technology of MgAPSO-31 zeolite catalyst and be not suitable for refinery propylene raw material.
The MCM-22 zeolite catalyst of Mobil/Badger process using Mobil exploitation, selectivity is very high, and the purity of product isopropyl benzene reaches 99.97%, and impurity such as ethylbenzene, n-proplbenzene and butylbenzene are all much lower than solid phosphoric acid method.This catalyst regeneration cycle is 2 years, and the life-span as long as five years.This technology is suitable for the transformation to alchlor process and two kinds of traditional technologys of solid phosphoric acid method.But do not see that this technology is applicable to the report of crude propylene.
The catalyzer of Dow/Kellog technology is the high-performance dealuminium mordenite, propylene almost 100% is transformed, and have shape selectivity, only generates the diisopropylbenzene(DIPB) of an a spot of contraposition and a position, and the massfraction of by product n-proplbenzene in product is less than 0.01%.This technology is particularly suitable for the transformation to solid phosphoric acid method technology, and production cost is lower.But do not see that this technology is applicable to the report of crude propylene.
The EniChem process using be that a kind of massfraction that contains is 60%～80% beta-zeolite catalyzer.Decaying catalyst can be regenerated by air heating, and through 5 cycles uses, only the activity than live catalyst reduces by 5%.These process using fixed-bed reactor, processing condition are benzene/alkene mol ratio 7.4,150 ℃ of temperature, pressure 3.0MPa.But do not see that this technology is applicable to the report of crude propylene.
What Beijing Institute of Clothing Tech in 1998 and chemical industry two factories of Beijing yanshan petrochemical company limited developed jointly is the gas-liquid-solid three-phase method synthesizing iso-propylbenzene technology of catalyzer with modified beta zeolite FX-01, and industrial scale is the 85kt/a isopropyl benzene.But with respect to liquid phase method, this technology exists the lower problem of alkylated reaction propylene mass space velocity.Calendar year 2001 Yan Hua company succeeds in developing liquid phase method synthesizing iso-propylbenzene technology, and the trade mark that adopts Beijing Institute of Clothing Tech's chemical institute and chemical industry two factories of Yan Hua company to develop jointly is the modified beta zeolite catalyst of FHI-01, and industrial scale is the 68kt/a isopropyl benzene.This technical process is reasonable, smooth operation, and catalyst productivity improves a lot than the liquid-solid trichotomy of Primordial Qi, and isopropyl benzene selectivity and product purity all satisfy industrial requirement.But when adopting crude propylene to make raw material, catalyzer is easy to inactivation, and the regeneration period is short, so this technology is not suitable for refinery propylene raw material.
Crude propylene derives from refinery, and with respect to the cracking propylene, the big advantage such as inexpensive of the amount of having if can replace the raw material of cracking propylene as alkylated reaction, will reduce production costs, and increases the business economic benefit, has also enlarged the purposes of crude propylene simultaneously.Therefore, each company all makes raw material attempting to adopt crude propylene to replace the cracking propylene now.But because crude propylene derives from heavy oil fluid catalytic cracking, it is formed far beyond cracking propylene complexity, and foreign matter content is also high, unsuitable direct raw material as alkylated reaction.Problems such as when existing process using crude propylene was raw material, it was fast all to exist catalyst deactivation, and the regeneration period is short.
Summary of the invention
The objective of the invention is to overcome the deficiency of using refinery propylene raw material in the prior art, providing a kind of is raw material, the method that adopts the liquid phase method synthesizing iso-propylbenzene with the crude propylene.
Of the present invention by benzene and propylene through the method for alkylated reaction synthesizing iso-propylbenzene, comprise the following steps:
(1) refinery propylene raw material enters hydrogenator and carries out selective hydrogenation reaction, removes wherein alkynes and diolefine;
(2) purify pretreated refinery propylene raw material through step (1) and enter alkylation reactor, under catalyst action,, generate isopropyl benzene with benzene generation alkylated reaction.
Described refinery propylene raw material is before entering alkylation reactor, at first enter hydrogenator, purify pre-treatment,, make outlet alkynes or diene content＜5ppm to remove other alkynes or diolefine such as propine, propadiene (MAPD) and divinyl wherein.
Described refinery propylene raw material is carried out selective hydrogenation reaction under carbon three liquid phase hydrogenating catalyst effects, hydrogenation conditions is: temperature of reaction is 50-70 ℃, and reaction pressure is 2.5-3.5MPa, and the propylene mass space velocity is 25-45h
-1, hydrogen alkynes is than being 1.1-1.5.Hydrogenator is equipped with carbon three liquid phase hydrogenating catalysts, as palladium series catalyst, but effective elimination alkynes or diolefine.
Described process purifies pretreated refinery propylene raw material and enters alkylation reactor, under the effect of catalyzer, generate isopropyl benzene and a small amount of diisopropylbenzene(DIPB) with benzene generation alkylated reaction, transalkylation reaction can take place and regenerate isopropyl benzene in diisopropylbenzene(DIPB) and benzene, can obtain the product isopropyl benzene through rectifying separation again.The catalyzer that wherein said alkylation reactor is packed into is molecular sieve catalyst or any available solid acid catalyst, and propylene conversion can reach more than 99%, and the isopropyl benzene selectivity can reach more than 90%.
Alkylation reactor of the present invention is multi-stage fixed-bed reactor, propylene and benzene sectional feeding, and the reactor outlet reaction solution partly circulates.The charge ratio of reactor is: fresh benzene/propylene mol ratio is 3-6, and recycle ratio is 1-3, and reaction bed total benzene alkene mol ratio that enters the mouth can reach more than 20.Described alkylation reaction condition is as follows: the propylene mass space velocity is 0.4-1.1h
-1, temperature of reaction is 140-170 ℃, reaction pressure is 2.5-3.5MPa.
Preferred method of the present invention comprises the following steps:
(1) refinery propylene raw material 18 is through preheaters 14 preheatings, to temperature be 40-50 ℃;
(2) enter hydrogenator 15 through the raw material propylene of preheating and carry out selective hydrogenation reaction with hydrogen 19, remove wherein alkynes or diolefine, the content that makes outlet alkynes or diolefine is less than 5ppm;
(3) enter preheater 16 through purifying pretreated refinery propylene raw material, being preheated to temperature is 100-120 ℃;
(4) material of drawing from step (3) preheater enters alkylation reactor 17, with benzene 20 alkylated reaction takes place under catalyst action, generates isopropyl benzene 21.
Existing liquid phase method synthesizing iso-propylbenzene technology is easy to adopt method of the present invention to transform.Use method of the present invention need before alkylation reactor, increase a hydrogenator, and hydrogenation reaction pressure is close with alkylated reaction pressure, be 2.5-3.5MPa, hydrogenation reaction and alkylated reaction are complementary, therefore increase hydrogenator and change little existing technology.Because carbon three hydrogenation catalysts that hydrogenator uses have higher hydrogenation reaction air speed, its propylene mass space velocity is up to 25-45h
-1, be tens times of alkylated reaction air speed, thereby the needed catalyzer of hydrogenation reaction is less, hydrogenator is less, and existing technological transformation is easily gone less investment, instant effect.With 100kt/a isopropyl benzene device is example, if alkylated reaction propylene mass space velocity is got 1.1h
-1, then alkylation reactor need be adorned 4 tons of catalyzer; If hydrogenation reaction propylene mass space velocity is got 45h
-1, then hydrogenator only need be adorned catalyzer 100kg.Hydrogenator is no more than 0.5m
3, volume is very little.In addition, method of the present invention also is applicable to the crude propylene transformation of the gas-liquid-solid three-phase method synthesizing iso-propylbenzene technology that is raw material.
Refinery propylene raw material can be removed the trace impurity (alkynes and diolefine) that contains in the raw material propylene through the hydrogenation preprocessing process, has reduced the possibility of alkylation catalyst poisoning and deactivation; And in hydrogenation process, hydrogen is superfluous relatively with respect to alkynes or diene content, and excessive hydrogen enters alkylation reactor, can also slow down the coking deactivation of alkylation catalyst.With compare without the pretreated alkylation process of hydrogenation, the stability of alkylation catalyst greatly improves after the hydrogenation pre-treatment, the regeneration period obviously prolongs.Compare as raw material with the cracking propylene, refinery propylene raw material is after hydrotreatment, and the life-span of alkylation catalyst prolongs to some extent.
Therefore, the beneficial effect of the inventive method is as follows:
1, method of the present invention has solved the use crude propylene fully and has made problems such as raw material catalyst for alkylation reaction inactivation is fast, the regeneration period is short, and the further enhancing of the stability of alkylation catalyst, is difficult for inactivation, regeneration period is long, prolong entire life, and the device running is steady, and operational stability strengthens;
2, method of the present invention is strong to the adaptability of raw material, both has been applicable to that the cracking propylene makes raw material, is applicable to that also crude propylene makes raw material;
3, use method of the present invention, the alkylated reaction selectivity improves, and product isopropyl benzene purity is higher;
4, the existing gentle liquid-solid trichotomy technology of liquid phase method technology is easy to adopt method of the present invention to transform, less investment, instant effect.
Description of drawings
Fig. 1 is the Experimental equipment of the method for synthesizing iso-propylbenzene of the present invention.
Fig. 2 is the schematic flow sheet of the method by the crude propylene synthesizing iso-propylbenzene of the present invention.
Fig. 3 be when carrying out accelerated weathering test propylene conversion with the change curve in reaction times.
13 samplings place of 1 nitrogen steel cylinder, 2 hydrogen gas cylinders, 3 propylene steel cylinders, 4 hydrogenators, 5 alkylation reactors, 6 benzene bottles, 7 waste liquid bottles, 8 strainers, 9 reducing valve, 10 nitrogen flow meters, 11 propylene pumps, 12 benzene pumps
Embodiment
Embodiments of the invention and Comparative Examples are to adopt device shown in Figure 1 to carry out, alkylation reactor 5 is a stainless steel tubular type reactor, internal diameter is 22mm, filling 5 grams are mixed with equal-volume quartz sand by the HY-BI type alkylation catalyst that Huayu Tongfang Chemical Science and Technology Development Co., Ltd., Beijing provides.Hydrogenator 4 internal diameter 12mm, in adorn the BC-L-83 type hydrogenation catalyst that 5 grams are provided by the Beijing Chemical Research Institute.Reaction unit has temperature control and pressure control system, and benzene and propylene liquid adopt the charging of two micro-measurement pumps, and hydrogen feed is controlled by mass-flow gas meter.
The composition of raw material propylene is analyzed by Hewlett-Packard's 6890 gas chromatographs.Table 1 and table 2 have been listed the composition analysis result of crude propylene and cracking propylene.
Table 1 crude propylene composition analysis result
| Component | Ethene | Propylene | Butylene | Divinyl | Methane | Ethane | Propane | Propine |
| Mole fraction (%) | 0.24 | 95.4 | 0.74 | 0.01 | 0.03 | 0.05 | 0.55 | 1.07 |
Annotate: carbon more than 5 other impurity occupy 0.91%
Table 2 cracking propylene composition analysis result
| Component | Ethene | Propylene | Butylene | Divinyl | Methane | Ethane | Propane | Propine |
| Mole fraction (%) | 0 | 99.4 | 0.001 | 0 | 0 | 0 | 0.53 | 0.03 |
Annotate: carbon more than 5 other impurity occupy 0.03%
By analytical results as can be seen, contain more propine in the crude propylene,, think that propine is the major impurity that causes alkylation catalyst deactivation through inventor's further investigation.
Adopt to reduce benzene alkene mol ratio, promptly increase in the reaction feed quick aging method of propylene content catalyst life is estimated.Usually the selected benzene alkene mol ratio of accelerated deterioration is 2.Because accelerated life can reflect the practical life of catalyzer, promptly accelerated life is long more, and the practical life of catalyzer is long more, and vice versa, so experimental result has comparability.Contrasted as can be known by lab scale accelerated deterioration experiment and industrial real-world operation situation, if accelerated life is 24 hours, then the one way life-span of catalyzer was 2 years under the industrial condition.
Embodiment 1
Propylene feedstocks is a crude propylene, adopts method of the present invention, at first carries out the pre-treatment of propylene, makes propylene enter hydrogenator, and operational condition is: hydrogen alkynes is than 1.5,60 ℃ of temperature of reaction, reaction pressure 3.0MPa; Then, enter alkylation reactor through pretreated crude propylene, 140 ℃ of temperature of reaction, reaction pressure 3.0MPa, propylene mass space velocity 1.62h
-1, carry out alkylated reaction under the condition of benzene alkene raw materials components mole ratio 2.Experimental data is listed in table 3.Propylene conversion was with the change curve in reaction times when curve c carried out accelerated deterioration for using crude propylene again through hydrogenator among Fig. 3.
Comparative Examples 1
Use crude propylene to be raw material, propylene directly enters alkylation reactor and carries out the accelerated deterioration experiment without hydrogenator, and other reaction conditions is identical with embodiment 1, and experimental data is listed in table 3.Propylene conversion was with the change curve in reaction times when curve a carried out accelerated deterioration for using crude propylene without hydrogenator among Fig. 3.
Comparative Examples 2
Use the cracking propylene to be raw material, propylene directly enters alkylation reactor and carries out the accelerated deterioration experiment without hydrogenator, and other reaction conditions is identical with embodiment 1, and experimental data is listed in table 3.Propylene conversion was with the change curve in reaction times when curve b carried out accelerated deterioration for using the cracking propylene without hydrogenator among Fig. 3.
If be reduced to 60% of initial conversion with propylene conversion is the inactivation sign, then as can be seen by curve a, b among Fig. 3, in liquid phase method synthesizing iso-propylbenzene technology, the accelerated life of catalyzer is 24 hours when using the cracking propylene to make raw material, and use crude propylene to make raw material only is 12 hours, half when just being raw material with the cracking propylene.Illustrate that the impurity in the crude propylene produces very big influence to catalyst life in the liquid phase method synthesizing iso-propylbenzene.By curve c among Fig. 3 as can be seen, use crude propylene to make raw material, life of alkylation catalysts obviously improves behind the hydrogenation.Extend to 29 hours by original 12 hours, adopt the cracking propylene to do 24 hours life-spans of raw material when having surpassed not hydrogenation.Alkynes such as the propine that this explanation contains in crude propylene or diolefine have a significant impact the life-span of alkylation catalyst really; By hydrogenation reaction, alkynes or diolefine are changed alkene, can remove effectively influences the active impurity of alkylation catalyst, and the introducing of excess hydrogen has simultaneously also slowed down the coking deactivation of alkylation catalyst, thereby life of catalyst is prolonged.
Table 3 accelerated deterioration experimental data
| Reaction times (h) | Propylene conversion (%) | ||
| Comparative Examples 2 | Comparative Examples 1 | Embodiment 1 | |
| 1 | 14.332 | 17.350 | |
| 2 | 48.368 | 53.171 | 15.124 |
| 3 | 59.944 | 83.189 | 47.438 |
| 4 | 80.276 | 88.052 | 70.269 |
| 5 | 88.519 | 91.830 | 89.222 |
| 6 | 91.858 | 94.460 | |
| 7 | 94.978 | 90.367 | 97.928 |
| 8 | 95.594 | 88.669 | 98.209 |
| 9 | 96.938 | 84.813 | 98.704 |
| 10 | 92.000 | 80.266 | 96.648 |
| 11 | 96.499 | 70.689 | 97.861 |
| 12 | 96.155 | 48.305 | 99.237 |
| 13 | 95.775 | 99.857 | |
| 14 | 96.546 | 99.518 | |
| 15 | 97.744 | 94.946 | |
| 16 | 95.424 | 95.987 | |
| 17 | 95.278 | 97.246 | |
| 18 | 91.792 | 95.923 | |
| 19 | 89.953 | 95.479 | |
| 20 | 83.309 | 93.947 | |
| 21 | 81.603 | 94.765 | |
| 22 | 71.750 | 91.329 | |
| 23 | 65.250 | 90.303 | |
| 24 | 59.500 | 89.999 | |
| 25 | 83.603 | ||
| 26 | 79.037 | ||
| 27 | 71.162 | ||
| 28 | 63.707 | ||
| 29 | 56.869 | ||
Claims (8)
- One kind by benzene and propylene through the method for alkylated reaction synthesizing iso-propylbenzene, it is characterized in that this method comprises the following steps:(1) refinery propylene raw material enters hydrogenator and carries out selective hydrogenation reaction, removes wherein alkynes and diolefine;(2) purify pretreated refinery propylene raw material through step (1) and enter alkylation reactor, under catalyst action,, generate isopropyl benzene with benzene generation alkylated reaction.
- 2. the method for claim 1 is characterized in that described refinery propylene raw material carries out selective hydrogenation reaction under carbon three liquid phase hydrogenating catalyst effects, and the content that makes outlet alkynes and diolefine is less than 5ppm.
- 3. method as claimed in claim 2, it is characterized in that described hydrogenation conditions is: temperature of reaction is 50-70 ℃, and reaction pressure is 2.5-3.5MPa, and the propylene mass space velocity is 25-45h -1, hydrogen alkynes is than being 1.1-1.5.
- 4. the method for claim 1 is characterized in that described alkylation reactor is multi-stage fixed-bed reactor, raw material propylene and benzene sectional feeding, and the reactor outlet reaction solution partly circulates.
- 5. method as claimed in claim 4, it is characterized in that the charge ratio of described alkylation reactor reaction solution is: fresh benzene/propylene mol ratio is 3-6, outlet reaction solution internal circulating load is 1-3 with the ratio of fresh feed amount.
- 6. the method for claim 1, it is characterized in that described alkylation reaction condition is: the propylene mass space velocity is 0.4-1.1h -1, temperature of reaction is 140-170 ℃, reaction pressure is 2.5-3.5MPa.
- 7. the method for claim 1 is characterized in that described alkylation reactor uses molecular sieve catalyst or the solid acid catalyst that is applicable to alkylated reaction.
- 8. the method for claim 1 is characterized in that this method may further comprise the steps:(1) refinery propylene raw material is through the preheater preheating, to temperature be 40-50 ℃;(2) enter hydrogenator through the raw material propylene of preheating and carry out selective hydrogenation reaction, remove wherein alkynes or diolefine, the content that makes outlet alkynes or diolefine is less than 5ppm;(3) enter preheater through purifying pretreated refinery propylene raw material, being preheated to temperature is 100-120 ℃;(4) material of drawing from step (3) preheater enters alkylation reactor, with benzene generation alkylated reaction, generates isopropyl benzene under catalyst action.
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| CNB2003101034365A CN100363315C (en) | 2003-10-31 | 2003-10-31 | Method for synthesizing cumin from refinery propene |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101034365A CN100363315C (en) | 2003-10-31 | 2003-10-31 | Method for synthesizing cumin from refinery propene |
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| CN100363315C true CN100363315C (en) | 2008-01-23 |
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| CN110655435B (en) * | 2018-06-28 | 2022-06-24 | 中国石油化工股份有限公司 | Solid acid alkylation reaction method and reaction device |
| CN113721683B (en) * | 2020-05-25 | 2022-08-19 | 中国石油化工股份有限公司 | Automatic control method and equipment for carbon-three-liquid phase hydrogenation reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235146A (en) * | 1999-04-09 | 1999-11-17 | 中国石油天然气集团公司 | Method for preparing ethylbenzene and/or isopropylbenzene from thin ethylene and/or propylene |
| CN1123554C (en) * | 1998-05-14 | 2003-10-08 | 中国科学院大连化学物理研究所 | Process for preparing ethylbenzene and isopropylbenzene from low-concentration ethylene and propylene |
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2003
- 2003-10-31 CN CNB2003101034365A patent/CN100363315C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123554C (en) * | 1998-05-14 | 2003-10-08 | 中国科学院大连化学物理研究所 | Process for preparing ethylbenzene and isopropylbenzene from low-concentration ethylene and propylene |
| CN1235146A (en) * | 1999-04-09 | 1999-11-17 | 中国石油天然气集团公司 | Method for preparing ethylbenzene and/or isopropylbenzene from thin ethylene and/or propylene |
Non-Patent Citations (1)
| Title |
|---|
| 国产碳三液相加氢催化剂在乙烯装置上的应用. 朱宏林等.齐鲁石油化工，第29卷第4期. 2001 * |
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