CN101993333A - Combined method for increase production of paraxylene in arene production - Google Patents
Combined method for increase production of paraxylene in arene production Download PDFInfo
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- CN101993333A CN101993333A CN2009100578260A CN200910057826A CN101993333A CN 101993333 A CN101993333 A CN 101993333A CN 2009100578260 A CN2009100578260 A CN 2009100578260A CN 200910057826 A CN200910057826 A CN 200910057826A CN 101993333 A CN101993333 A CN 101993333A
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Abstract
The invention relates to a combined method for increase production of paraxylene in arene production, which is used for solving the problems that the paraxylene has low concentration in mixed paraxylene, circulating volume of arene treatment is large, requirements of reacting materials are rigorous, energy consumption is high and the like in the prior art in the paraxylene producition. The method is realized by comprising the following steps: adopting mixed materials separated by a reforming unit; feeding C9 arene and the third flow of benzene separated by the reforming unit into a benzene and C9 arene alkyl group transfer process unit for carrying out dealkylation reaction so as to generate second flow of benzene, toluene and C8 arene; feeding the second flow of benzene, oluene and C8 arene into a toluene selectivity dismutation process unit for carrying out toluene selectivity dismutation reaction to generate the C8 arene and benzene steam containing the paraxylene, and obtaining third flow of C8 arene, toluene and benzene, wherein the flow of toluene is returned to the toluene selectivity dismutation process unit; delivering mixture of first flow of C8 arene, second flow of C8 arene and fourth flow of C8 arene to an adsorption separation unit with 12-36 adsorbent bed layers to obtain products of first flow of paraxylene; and delivering the third flow of C8 arene to a crystallization separation unit to obtain products of the fourth flow of C8 arene and the second flow of paraxylene. The above problems can be preferably solved by the technical scheme, and the technical scheme can be used for industrial production of the paraxylene.
Description
Technical field
The present invention relates to the combined method of volume increase p-Xylol in a kind of aromatic hydrocarbons production.
Background technology
P-Xylol is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resins, agricultural chemicals, medicine, plastics purposes is widely arranged.Typical p-Xylol production method is that the dimethylbenzene that contains ethylbenzene of the thermodynamic(al)equilibrium that generates from the petroleum naphtha catalytic reforming is to separate or molecular sieve simulated moving bed adsorption separation (abbreviation fractionation by adsorption) technology by multistage cryogenic crystallization the C8 aronmatic, and p-Xylol is separated from the close with it isomer mixture of boiling point.And, often take C for the processing of the dimethylbenzene of an ortho position and a position
8A isomerization (abbreviation isomerization) technology makes it isomery and turns to p-Xylol.In order to increase production p-Xylol, utilize toluene disproportionation or toluene and carbon nine and above aromatic disproportion thereof and transalkylation (being called for short toluene disproportionation and transalkylation) reaction to generate benzene and C
8A, thereby volume increase C
8A is the operational path that effectively increases production p-Xylol.
Up to now, in the world more typically, also the technology relevant with toluene disproportionation of comparative maturity has sixties Mo industrialized Tatoray tradition toluene disproportionation process, the MTDP of late nineteen eighties release and S-TDT technology and the TransPlus technology of releasing in recent years.Selective disproportionation of toluene is a new way of producing p-Xylol.Because toluene is at the C that can carry out selective disproportionation generation benzene and high p-Xylol concentration on the ZSM-5 of modification catalyzer
8Therefore A only needs can isolate most p-Xylol through simple once the step subzero fractionation.In recent years, along with improving constantly of catalyst performance, this technology has obtained considerable progress.Its typical process has industrialized MSTDP selective disproportionation of toluene technology and the pX-Plus technology released in recent years the late nineteen eighties.
Industrialized selective disproportionation of toluene technology-MSTDP is the catalyst treatment methylbenzene raw material with treated ZSM-5 type mesoporous molecular sieve, can obtain the C of high p-Xylol concentration (85～90%, weight percent, identical except that indicating below)
8The benzene of A and nitration grade.Do not see the PX-plus technology of industrial application report as yet, its main technique index is that the selectivity of pX reaches 90% in the dimethylbenzene under toluene conversion 30% condition, and the mol ratio of benzene and pX is 1.37.
Yet, in the technology of this class selective disproportionation of toluene, in the harshness of the simultaneous with high para-selectivity to material choice.This type of technology can only be raw material with toluene, and C
9 +A does not have purposes in this technology, can not directly be utilized at least, causes the waste of aromatic hydrocarbon resource.In addition, this technology is a large amount of benzene of by-product also, causes the p-Xylol yield on the low side, and this is the fatal shortcoming of selective disproportionation technology.
The reactor feed of typical Tatoray technology is to be reaction raw materials with toluene and C9 aromatic (C9A).The dimethylbenzene that is generated by Tatoray technology is to be in the isomer mixture that thermodynamic(al)equilibrium is formed, and has the p-Xylol content of industrial application value generally to have only about 24% most.For the xylol this point that selective disproportionation of toluene can obtain the p-Xylol concentration about 90%, Tatoray technology is in tangible inferior position undoubtedly, but Tatoray technology is exactly that Tatoray technology can be converted into benzene and dimethylbenzene to C9A with respect to one of selective disproportionation of toluene technology very big advantage.Document based on Tatoray technology has USP4341914, Chinese patent 98110859.8, USP2795629, USP3551510, Chinese patent 97106719.8 etc.The technical process that representative USP4341914 proposes is for to carry out the aromatic hydrocarbons fractionation with reformate, toluene that obtains and C
9A enters the Tatoray technique unit and carries out disproportionation and a heatable brick bed group-transfer reaction, and resultant of reaction is toluene and C after separating
9A and part carbon ten (C
10A) circulation, benzene is as the product extraction, C8 aronmatic and the C8 aronmatic from isomerization unit enter the pX tripping device together and isolate highly purified p-Xylol product, and other C8 aronmatic isomer carries out the xylol that xylene isomerization reaction obtains being in thermodynamic(al)equilibrium again to isomerization unit.
Heavy aromatics takes off alkyl and produces C
6～C
8Aromatic hydrocarbons technology caused people's attention gradually along with the rise of selective disproportionation of toluene technology in the last few years.USP5763721 and USP5847256 have proposed to be used for the catalyzer of heavy aromatics dealkylation respectively.Wherein, USP5847256 has announced a kind of mordenite catalyst of rhenium-containing, and this catalyzer is specially adapted to transform and contains the many raw materials of ethyl, can obtain products such as toluene, dimethylbenzene and benzene.
C
8The boiling point of each component of aromatic hydrocarbons is approaching: 136.2 ℃ in ethylbenzene, 138.4 ℃ of p-Xylol, 139.1 ℃ of m-xylenes, 144.4 ℃ of o-Xylols, the o-Xylol that its mid-boiling point is the highest can be separated by rectification method, need up to a hundred theoretical stages and bigger reflux ratio, the ethylbenzene that boiling point is minimum also can separate by rectification method, but much more difficult.C
8The fusing point of each component of aromatic hydrocarbons has bigger gap: 13.3 ℃ of p-Xylol, o-Xylol-25.2 ℃, m-xylene-47.9 ℃, ethylbenzene-94.95 ℃.Wherein the fusing point of p-Xylol is the highest, can adopt crystallization process that p-Xylol is wherein separated, and is not high as p-Xylol concentration in the raw material, for reaching the acceptable yield of industrial production, generally adopts two sections crystallizations.USP3177255, USP3467724 at first crystallize out most p-Xylol under-80～-60 ℃ low temperature and make productive rate reach theoretical maximum, this moment crystal purity between 65～85%, the crystallization second time is being carried out in the fusing back; Tc can obtain the p-Xylol of 99% above purity generally at-20～0 ℃ for the second time, and p-Xylol content is higher in the mother liquor, can return crystallized region recycle for the first time.
Utilize sorbent material to C
8Each component of aromatic hydrocarbons is difference optionally, can p-Xylol be separated by adsorption method of separation, after this method realizes industrialization in nineteen seventies for producing the main method of p-Xylol.USP2985589 has described the method for utilizing the simulation moving-bed separating paraxylene of adverse current; USP3686342, USP3734974, CN98810104.1 have described sorbent material that fractionation by adsorption uses X or the Y zeolite as barium type or barium potassium type; USP3558732, USP3686342 use toluene and the p-Diethylbenzene desorbing agent as fractionation by adsorption respectively.
Summary of the invention
Technical problem to be solved by this invention be in the conventional art when producing p-Xylol, exist owing to p-Xylol concentration in the xylol is low, cause problems such as dimethylbenzene separating unit and isomerization unit internal circulating load are big, energy consumption height, a kind of new p-Xylol production method is provided.This method is with benzene, toluene, C
8A and C
9 +A is that raw material is produced p-Xylol, improves the concentration of p-Xylol in the xylol, reduces the scale of p-Xylol separating unit, isomerization unit and aromatic hydrocarbons fractionation unit greatly, thereby reduces the energy consumption of whole device.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the combined method of volume increase p-Xylol during a kind of aromatic hydrocarbons is produced may further comprise the steps:
A. separate the mixing raw material that contains benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics from reformer unit, isolate first strand of benzene, first strand of toluene, first burst of C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics;
B.a) the isolated C9 aromatic of step and the 3rd strand of benzene enter benzene and C9 aromatic alkyl transfering process unit, carry out dealkylation under hydro condition, generate second strand of benzene, second strand of toluene and second strand of C8 aronmatic;
C. first strand of toluene and second strand of toluene enter the selective disproportionation of toluene technique unit together, under hydro condition, carry out toluene selective disproportionation reaction, the reaction back generates C8 aronmatic and the benzene logistics that contains p-Xylol, after separating, obtain the 3rd strand of C8 aronmatic, the 3rd strand of toluene and the 3rd strand of benzene, wherein the 3rd strand of toluene turns back to the selective disproportionation of toluene technique unit;
D. send into the adsorption separation unit that contains 12～36 adsorption bed after first strand of C8 aronmatic, second strand of C8 aronmatic and the 4th strand of C8 aronmatic mix, obtain first strand of p-Xylol product;
E. the 3rd strand of C8 aronmatic sent into the Crystallization Separation unit, obtains the 4th strand of C8 aronmatic and second strand of p-Xylol product.
In technique scheme, the used catalyzer in selective disproportionation of toluene unit is the type ZSM 5 molecular sieve catalyzer, type ZSM 5 molecular sieve contains at least a metal or its oxide compound that is selected from platinum, molybdenum or the magnesium, and its consumption is 0.005～5% by weight percentage; The operational condition of selective disproportionation of toluene technique unit is as follows: reaction pressure is 1～4MPa, and temperature of reaction is 300～480 ℃, and hydrogen/hydrocarbon mol ratio is 0.5～10, and the liquid weight air speed is 0.8～8 hour
-1The used catalyzer in benzene and C9 aromatic alkyl transfering process unit is at least a molecular sieve that is selected among beta-zeolite, mordenite or the MCM-22, and bismuthiferous metal or its oxide compound in the catalyzer, its consumption are 0.005～5% by weight percentage; Benzene and the unitary operational condition of C9 aromatic alkyl transfering process are as follows: reaction pressure is 1～6MPa, and temperature of reaction is 300～600 ℃, and hydrogen/hydrocarbon mol ratio is 2～10, and weight space velocity is 0.5～3 hour
-1The p-Xylol separating unit adopts fractionation by adsorption and the Crystallization Separation separating paraxylene that combines, and Crystallization Separation can adopt film-falling crystallization to separate or suspension crystallization separates.The adsorption bed number of plies of adsorption separation unit is preferably 20～30.The isolating Tc of film-falling crystallization is-30～5 ℃; The isolating Tc of suspension crystallization is-15～5 ℃, and washings/crystal weight ratio is 0.05～0.5; The purity of p-Xylol product is p-Xylol weight concentration 〉=99.8%.
Among the present invention, in benzene and C9 aromatic alkyl transfering process unit, owing to use bismuthiferous zeolite to be catalyzer, under hydro condition, by transalkylation reaction, effectively with reaction raw materials benzene and C
9Aromatic hydrocarbons has changed into dimethylbenzene, has realized the raw material processing flexibility, and aromatics conversion rate reaches 64.8%, and selectivity reaches 90%, the C that reaction generates
8A then enters fractionation by adsorption and isomerization unit is produced pure p-Xylol.Toluene other toluene in Aromatic Hydrocarbon United Plant that carbon nine and above aromatic hydrocarbons thereof take off the generation of alkyl technique unit enters the selective disproportionation of toluene unit, under the effect of platiniferous ZSM-5 catalyzer, toluene selective disproportionation reaction takes place, generate benzene and the xylol that contains the high density p-Xylol, p-Xylol concentration can reach 80～95%, this xylol is sent to the Crystallization Separation unit and obtains pure p-Xylol, and the residue xylol also enters fractionation by adsorption and isomerization unit is produced pure p-Xylol.As can be seen, such operational path can allow the concentration of producing p-Xylol in the xylol that obtains significantly improve, and has made full use of C again
9 +The A resource has reduced the treatment scale of isomerization unit and adsorption separation unit, has reduced energy consumption and facility investment scale effectively, and has reduced production cost, has obtained better technical effect.
Description of drawings
Fig. 1 is the technical process of traditional p-Xylol production equipment.
Fig. 2 is the combination process flow process of volume increase p-Xylol in the aromatic hydrocarbons production of the present invention.
I is the reformer unit deheptanizer among Fig. 1 or Fig. 2; II is the Aromatics Extractive Project unit; III is the benzene toluene separative element after the extracting; IV is the benzenol hydrorefining unit; V is toluene disproportionation and alkyl transfering process unit; VI is the selective disproportionation technique unit; VII is benzene and C9 aromatic alkyl transfering process unit; VIII is the xylene isomerization process unit; IX is adsorption separation unit; X is the aromatic hydrocarbons fractionation unit of selective disproportionation; XI is the Crystallization Separation unit. 1 is the reformation de-pentane oil, and 2 is the C that distillates from the deheptanizer cat head7 -(comprising that benzene, toluene and carbon six carbon seven are non-aromatic), 3 carbon eight and above arene streams for the extraction of deheptanizer tower reactor, 4 for extracting benzene and the toluene logistics after non-aromatic, 5 is non-aromatic, 6 is the high purity product benzene that the benzene column overhead after the extracting is extracted, 7 is the toluene that the toluene tower cat head after the extracting is extracted, 8 C for the extraction of the toluene tower reactor after the extracting8 +A, 9 is disproportionation and transalkylation product stream, 10 is C8 +The C that heavy aromatics column overhead in the A fractionation unit is extracted out9A and part C10A, 11 is the mixed xylenes of extracting out from the benzenol hydrorefining cat head, 12 is the C that heavy aromatics Tata still is extracted out10A, 13 for heavy aromatics takes off the still liquid that alkyl unit benzene Tata still is extracted out, 14 a small amount of toluene of separating for adsorption separation unit, the 15 pure paraxylene of separating for adsorption separation unit, 16 for adsorbing separation goes out mixed xylenes behind the PX, and 17 is the C that isomerization unit deheptanizer tower reactor is discharged8 +The A logistics, 18 logistics that contain benzene and toluene of extracting for isomerization unit deheptanizer cat head, 19 is the benzene logistics of disproportionation and transalkylation extraction, the 20 nitrated benzene of extracting for the benzene column overhead of selective disproportionation aromatic hydrocarbons fractionation unit, 21 toluene of extracting for the toluene tower cat head of selective disproportionation aromatic hydrocarbons fractionation unit, 22 C that extract for the benzenol hydrorefining cat head of selective disproportionation aromatic hydrocarbons fractionation unit8 +A, 23 is the still liquid that the benzenol hydrorefining tower reactor of selective disproportionation aromatic hydrocarbons fractionation unit is extracted out, the 24 pure paraxylene of separating for the Crystallization Separation unit, 25 go out mixed xylenes behind the PX for Crystallization Separation.
The technological process of tradition paraxylene process units as shown in Figure 1. Enter deheptanizer I from reformation depentanizer tower bottoms 1, cat head is told carbon seven and following aromatic hydrocarbons non-aromatics logistics 2 thereof and is entered Aromatics Extractive Project unit II and carry out separating of aromatic hydrocarbons and non-aromatics, isolated non-aromatic 5 discharge, unit III is removed in benzene toluene logistics 4, the benzene column overhead of products benzene 6 after the extracting sent, and the toluene tower tower reactor of mixed xylenes 8 after the extracting extracted out and entered benzenol hydrorefining unit IV. In addition, deheptanizer tower reactor logistics 3 also enters benzenol hydrorefining unit IV, mix carbon eight logistics 11 and distillate p-xylene separation unit IX from cat head, C9 aromatic 10 and from the raw material of the isolated toluene logistics 7 of toluene tower cat head as toluene disproportionation and transalkylation II, C10 +A logistics 12 is sent as byproduct; Disproportionation directly enters unit III with 9 of transalkylation product streams and separates; Adsorption separation unit IX isolates purpose product paraxylene 15, and a small amount of toluene 14 returns toluene disproportionation unit VI, and other mixed xylenes 16 enters xylene isomerization unit VIII and carries out isomerization reaction, the C that isomerization unit deheptanizer tower reactor is discharged8 +A logistics 17 is sent to benzenol hydrorefining unit IV, and the logistics that contains benzene and toluene 18 that the deheptanizer cat head is extracted is sent to the catalytic reforming unit.
The group technology flow process that paraxylene of the present invention is produced as shown in Figure 2. Be that with the improvements of traditional handicraft technology of the present invention changes the toluene disproportionation process unit in the traditional handicraft into C9 aromatic and takes off the alkyl technique unit, in addition, a cover selective disproportionation of toluene unit VI, corresponding aromatic hydrocarbons fractionation unit X and Crystallization Separation unit XI have been increased. The place that Fig. 2 is identical with Fig. 1 is no longer narrated, and only elaborates with regard to difference below. The benzene 20 that in the technology of the present invention the former carbon nine that is used as toluene disproportionation and transalkylation raw material and above aromatic hydrocarbons 10 thereof and selective disproportionation unit is generated is as the raw material of benzene and C9 aromatic alkyl transfering process unit, benzene logistics 7 (comprising the toluene that the toluene brought in the raw material and reaction generate) is all as the raw material of selective disproportionation unit, from the nitrated benzene 20 of benzene column overhead extraction, toluene tower overhead extraction toluene 21 turns back to selective disproportionation unit VI, the still liquid 23 that the benzenol hydrorefining tower reactor is extracted out is sent into benzenol hydrorefining unit IV, dimethylbenzene cat head extraction C8 +Crystallization Separation unit XI is sent in A logistics 22, logistics 22, isolates pure paraxylene 24, and other mixed xylenes 25 is delivered to adsorption separation unit IX.
The present invention is further illustrated below by specific embodiment, and still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
By flow process shown in Figure 2, with C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate ability and each unitary treatment scale situation that the present invention produces p-Xylol and benzene.Typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted sees Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, and the filling bismuth-containing is 0.05% beta-zeolite catalyzer in the reactor, and reaction conditions is: 385 ℃ of temperature of reaction, pressure are 3.0MPa, and weight space velocity is 2.0 hours
-1, hydrogen/hydrocarbon mol ratio is 3.0.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A generates benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and filling contains 0.05% platinum ZSM-5 molecular sieve catalyst in the reactor, and reaction conditions is: 385 ℃ of temperature of reaction, pressure are 3.0MPa, and weight space velocity is 2.0 hours
-1, hydrogen/hydrocarbon mol ratio is 3.0.Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A.
24 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in the moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts film-falling crystallization to separate, and Crystallization Separation is divided crystallization, sweating and three steps of fusion, and wherein Tc is-20 ℃, and sweating temperature is 15 ℃, and melt temperature is 30 ℃.
Table 1 reformation de-pentane oil aromatic hydrocarbons is formed and flow rate
| Form | Ben | Tol | C 8A | C 9A | C 10 + | ∑ |
| Form weight % | 14.41 | 26.79 | 33.53 | 24.02 | 1.25 | 100.00 |
| Flow, kilogram/hour | 12673 | 23560 | 29482 | 21122 | 1095 | 87932 |
Wherein: NA is a non-aromatics, and Ben is a benzene, and Tol is a toluene, C
8A is a C8 aronmatic, C
9A is a C9 aromatic, C
10 +A is carbon ten and above aromatic hydrocarbons thereof, below identical.
According to aromatic hydrocarbons flow rate (fresh feed) in accompanying drawing 2 described technical process of the present invention and the table 1 and the operation of the parameter among the embodiment, the material charging and the discharging data of selective disproportionation of toluene unit, benzene and C9 aromatic transalkylation and isomerization unit are listed in table 2.Each unitary treatment scale of p-Xylol production equipment sees Table 3, and the output of product p-Xylol and benzene sees Table 4, and wherein the p-Xylol product increases by 19% with respect to Comparative Examples.
Table 2 embodiment 1 process stream table
Annotate: C
8A* is meant other C8 aronmatic except that PX, and is as follows.
Table 3 embodiment 1 each cell processing scale table
Table 4 embodiment 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 58591 | 13060 | 71651 |
| Purity, % | 99.80 | 99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technology of the present invention can be produced p-Xylol and benzene is 78324 kilograms/hour.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 26%, 27% and 27% respectively, and this has obviously reduced the Design of device scale.Plant energy consumption is 19890 * 10
6Joule/ton (p-Xylol+benzene) is with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), energy consumption has reduced by 25%.Therefore, problems such as xylol concentration was low when patent of the present invention had overcome the production p-Xylol that exists in the conventional art, internal circulating load is big, energy consumption height, the method that provides a kind of brand-new more economical being used to produce p-Xylol.
[embodiment 2]
By flow process shown in Figure 2, with C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate ability and each unitary treatment scale situation that the present invention produces p-Xylol and benzene.Typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted sees Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the Hydrogen MCM-22 zeolite catalyst of filling bismuth-containing 0.30% in the reactor, and reaction conditions is: 460 ℃ of temperature of reaction, pressure are 41.0MPa, weight space velocity is 3.0 hours
-1, hydrogen/hydrocarbon mol ratio is 8.0.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A generates benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, filling platiniferous 0.2% and 0.5% magnesium ZSM-5 molecular sieve catalyst in the reactor, and reaction conditions is: 450 ℃ of temperature of reaction, pressure are 6.0MPa, weight space velocity is 6.0 hours
-1, hydrogen/hydrocarbon mol ratio is 8.0.Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A.
30 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in the moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is 5 ℃.
Operate according to the parameter that provides in accompanying drawing 2 described technical process of the present invention and the example, each unitary treatment scale of p-Xylol production equipment sees Table 5, and the output of product p-Xylol and benzene sees Table 6.
Table 5 embodiment 2 each cell processing scale table
Table 6 embodiment 2 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 58591 | 13060 | 71651 |
| Purity, weight % | 99.80 | 99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technology of the present invention can be produced p-Xylol and benzene is 78340 kilograms/hour.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 26%, 26% and 24% respectively, has obviously reduced the Design of device scale.Plant energy consumption is 20465 * 10
6Joule/ton (p-Xylol+benzene) is with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), energy consumption has reduced by 23%.
[embodiment 3]
By flow process shown in Figure 2, with C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate ability and each unitary treatment scale situation that the present invention produces p-Xylol and benzene.Typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted sees Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the h-mordenite catalyzer of filling bismuth-containing 0.10% in the reactor, and reaction conditions is: 320 ℃ of temperature of reaction, pressure are 1.0MPa, weight space velocity is 0.8 hour
-1, hydrogen/hydrocarbon mol ratio is 2.0.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A generates benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and filling contains 0.3% molybdenum and 0.8% magnesium ZSM-5 molecular sieve catalyst in the reactor, and reaction conditions is: 320 ℃ of temperature of reaction, pressure are 1.0MPa, and weight space velocity is 0.8 hour
-1, hydrogen/hydrocarbon mol ratio is 1.0.Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A.
18 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in the moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is-15 ℃.
Operate according to the parameter that provides in accompanying drawing 2 described technical process of the present invention and the example, each unitary treatment scale of p-Xylol production equipment sees Table 7, and the output of product p-Xylol and benzene sees Table 8.
Table 7 embodiment 3 each cell processing scale table
Table 8 embodiment 3 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 58624 | 13060 | 71684 |
| Purity, weight % | 99.80 | 99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technology of the present invention can be produced p-Xylol and benzene is 71684 kilograms/hour.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 26%, 26% and 24% respectively, has obviously reduced the Design of device scale.Plant energy consumption is 21530 * 10
6Joule/ton (p-Xylol+benzene) is with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), energy consumption has reduced by 19%.
[comparative example 1]
By flow process shown in Figure 1, still with typical reformation de-pentane oil C in the table 1
6A～C
10 +The flow rate of A logistics is a basic data, investigates traditional ability that contains toluene disproportionation and unitary Aromatic Hydrocarbon United Plant production p-Xylol of alkyl transfering process and benzene as shown in Figure 1.The material charging and the extraction situation of its disproportionation and transalkylation, isomerization unit see Table 9, and each unitary treatment scale sees Table 10, and the output of product p-Xylol and benzene sees Table 11.
Table 9 comparative example 1 process stream table
Table 10 comparative example 1 each cell processing scale table
Table 11 comparative example 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 54316 | 22751 | 77067 |
| Purity, % | 99.80 | 99.94 |
The result shows, traditional aromatic hydrocarbons production technique reaction aroamtic hydrocarbon raw material listed as table 1, and the total amount that the worker has produced p-Xylol and benzene is 77067 kilograms/hour, plant energy consumption is 26579 * 10
6Kilojoule/ton (p-Xylol+benzene).
Claims (9)
1. the combined method of volume increase p-Xylol during an aromatic hydrocarbons is produced may further comprise the steps:
A. separate the mixing raw material that contains benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics from reformer unit, isolate first strand of benzene, first strand of toluene, first burst of C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics;
B.a) the isolated C9 aromatic of step and the 3rd strand of benzene enter benzene and C9 aromatic alkyl transfering process unit, carry out dealkylation under hydro condition, generate second strand of benzene, second strand of toluene and second strand of C8 aronmatic;
C. first strand of toluene and second strand of toluene enter the selective disproportionation of toluene technique unit together, under hydro condition, carry out toluene selective disproportionation reaction, the reaction back generates C8 aronmatic and the benzene logistics that contains p-Xylol, after separating, obtain the 3rd strand of C8 aronmatic, the 3rd strand of toluene and the 3rd strand of benzene, wherein the 3rd strand of toluene turns back to the selective disproportionation of toluene technique unit;
D. send into the adsorption separation unit that contains 12～36 adsorption bed after first strand of C8 aronmatic, second strand of C8 aronmatic and the 4th strand of C8 aronmatic mix, obtain first strand of p-Xylol product;
E. the 3rd strand of C8 aronmatic sent into the Crystallization Separation unit, obtains the 4th strand of C8 aronmatic and second strand of p-Xylol product.
2. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, it is characterized in that the used catalyzer in selective disproportionation of toluene unit is the type ZSM 5 molecular sieve catalyzer, type ZSM 5 molecular sieve contains at least a metal or its oxide compound that is selected from platinum, molybdenum or the magnesium, and its consumption is 0.005～5% by weight percentage.
3. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, the operational condition that it is characterized in that the selective disproportionation of toluene technique unit is as follows: reaction pressure is 1～4MPa, temperature of reaction is 300～480 ℃, hydrogen/hydrocarbon mol ratio is 0.5～10, and the liquid weight air speed is 0.8～8 hour
-1
4. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, it is characterized in that the used catalyzer in benzene and C9 aromatic alkyl transfering process unit is at least a molecular sieve that is selected among beta-zeolite, mordenite or the MCM-22, bismuthiferous metal or its oxide compound in the catalyzer, its consumption are 0.005～5% by weight percentage.
5. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, it is characterized in that benzene and the unitary operational condition of C9 aromatic alkyl transfering process are as follows: reaction pressure is 1～6MPa, temperature of reaction is 300～600 ℃, hydrogen/hydrocarbon mol ratio is 2～10, and weight space velocity is 0.5～3 hour
-1
6. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, it is characterized in that the p-Xylol separating unit adopts fractionation by adsorption and the Crystallization Separation separating paraxylene that combines, Crystallization Separation can adopt film-falling crystallization to separate or suspension crystallization separates.
7. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, the adsorption bed number of plies that it is characterized in that adsorption separation unit is 20～30.
8. the combined method of volume increase p-Xylol is characterized in that the isolating Tc of film-falling crystallization is-30～5 ℃ in producing according to the described aromatic hydrocarbons of claim 1; The isolating Tc of suspension crystallization is-15～5 ℃, and washings/crystal weight ratio is 0.05～0.5.
9. the combined method of volume increase p-Xylol in producing according to the described aromatic hydrocarbons of claim 1, the purity that it is characterized in that the p-Xylol product is p-Xylol weight concentration 〉=99.8%.
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| CN109970503A (en) * | 2017-12-27 | 2019-07-05 | 中国石油化工股份有限公司 | A kind of refining methd and refining system of paraxylene crude product |
| CN112169373A (en) * | 2019-07-05 | 2021-01-05 | 中国石油化工股份有限公司 | Method for adsorbing and separating target product by simulated moving bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109970503A (en) * | 2017-12-27 | 2019-07-05 | 中国石油化工股份有限公司 | A kind of refining methd and refining system of paraxylene crude product |
| CN109970503B (en) * | 2017-12-27 | 2023-11-24 | 中国石油化工股份有限公司 | Refining method and refining system for paraxylene crude product |
| CN112169373A (en) * | 2019-07-05 | 2021-01-05 | 中国石油化工股份有限公司 | Method for adsorbing and separating target product by simulated moving bed |
| CN112169373B (en) * | 2019-07-05 | 2022-03-11 | 中国石油化工股份有限公司 | Method for adsorbing and separating target product by simulated moving bed |
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