TW200533651A - Process and apparatus for the removal of nitrogen compounds from a fluid stream - Google Patents

Abstract

Disclosed is a process and apparatus for removing nitrogen compounds from an alkylation substrate such as benzene. A conventional adsorbent bed (46, 114) can be used to adsorb basic organic nitrogen compounds and a hot adsorbent bed (72, 162) of acidic molecular sieve can adsorb the weakly basic nitrogen compounds such as nitriles. Water facilitates the adsorption of the weakly basic nitrogen compounds. Running an alkylation substrate stream (68, 8) from a fractionation column (40, 130) of elevated temperature and suitable water concentration to the hot adsorbent bed may be advantageous.

Description

200533651 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method and a device for producing nitrogen compounds from L compounds to removing nitrogen compounds. In particular, the present invention conveys the η-f threshold to selectivity. The application of the adsorption method is to remove the riding class with Fe> IL, and #, ^ 保 道 方 香 No conversion catalyst. Another object of the present invention is to provide a hydration-enhancing bed that absorbs nitriles from the hydrocarbon feed stream in the alkylation or escape metathesis zone in the presence of water. Another objective of the present invention is to provide a protective bed for two different compositions that can cooperatively adsorb ONCs from a hydrocarbon feed stream. [Previous Technology] Molecular sieves are used as catalysts in aromatic conversion processes, and are well known in chemical processes and the refining industry. Commercially important aromatic conversion reactions include the alkylation of aromatic compounds, Shikou: in the production of ethyl toluene, xylene, ethyl ethyl, cumene, or high-carbon aromatic aromatics and disproportionation reactions For example: disproportionation of toluene, isomerization of xylene, or trans-firing of multi-base benzenes into monoalkylbenzenes. Generally, the feed to the aromatic conversion process will include aromatic components or calcined substrates, such as: benzene, and c2K2Q olefin calcining agents, multi-carbon based aromatic hydrocarbon converting agents. In the firing zone, the feedstock stream and the smoke-based feedstream react on the alkylation catalyst to produce alkylated benzenes, such as ethylbenzene or isopropylbenzene. Polyalkylbenzenes are separated from the monoalkylbenzene product and recovered to the transalkylation zone and contacted with benzene on the transalkylation catalyst to produce monoalkylbenzenes and benzene. Catalysts for such calcination or trans-calcination reactions typically include zeolite molecular sieves. U.S. Patent No. 1,891,458 discloses the existence of catalysts, including zeolites (3. US Patent 99299.doc 200533651 and US 5,03G, 786 discloses an aromatic conversion process using zeolite gamma and boiling μ molecular sieve catalysts. U.S. Patent No. 4,185,040 discloses the alkylation of benzene to produce ethylbenzene or cumene, using zeolites of molecular sieves such as χ, γ, [, B, ZSM-5 and ω. U.S. Patent No. 4,774, still Revealing an aromatic conversion process involving alkylation on a catalyst containing a solid phosphoric acid component, followed by transalkylation, using aluminosilicates including χ, γ, ultra-stable Y, L, ω, and mordenite Molecular sieves are converted to alkylation catalysts. Water is usually found in aromatic feeds in alkylation and transalkylation reactions, especially in benzene feeds. Benzene feeds are usually saturated with water, for example, when When recovering styrene monomer units, the molecular sieve catalysts used in the gasification or liquid phase calcination reaction will be sensitive to different amounts of water or sulfur compounds in the feed. The related patent US 4,1G7,224 discloses: If faster aging of the catalyst is acceptable, then in a gas phase reaction Water and hydrogen sulfide are tolerable. US patent US 5, () 3 (), 7_ shows that when the reaction zone is operated to maintain the reactor contents in the liquid phase, the feed is dehydrated to not more than water content ppm, and preferably 50 ppm or less. However, the two of WO 93 / ⑼ reveal that in the starting phase, the zeolite catalyst used in the alkylation or transalkylation process must have a minimum water content of not much. At 3.5% by weight, it is relative to the catalyst composition. EP 〇922 020 B1 discloses the use of a solid acid, which adsorbs impurities from a benzene alkylation feed, which is dried at a temperature between 13 ° C and 30 ° C To contain no more than 200 ppm of water to improve the life of the zeolite alkylation or transalkylation catalysts. Other impurities present in the feed to the aromatic conversion reactor, especially alkaline impurities such as alkali Organic nitrogen compounds (ONCs), neutralizing 98299.doc 200533651 including most of the solid acids of today's aromatic burning catalysts. And catalyst life is negatively affected. During the accumulation of nitrogen compounds ^ into: Even very low nitrogen compounds increase the frequency of catalyst regeneration, and Must be burned from the catalyst. More active zeolite catalysts are used in the aromatic conversion reaction. The impure nitrogen in the feed will reduce the catalyst life and must be controlled more carefully. Seek to reduce the amount of catalyst on the catalyst in the reaction area. Processes affected by nitrogen impurities. Test gas compounds that reduce catalyst life include + flowers, pyridines, quinoxanes, diethanolamine (DEA), morpholine, including n_methylamyl_M⑽M) and N_methyl _Tetrahydro NMp). Please delete it as an aromatic extractant and DEA is a corrosion inhibitor, which usually pollutes the aromatic feed stream. US Patent US 5,22M99 teaches the removal of ten quinones and quinoids with zeolites. The phthaloline and pyridine impurities were desorbed from the zeolite using toluene and dissolved water. Woo Na showed that the benzene zeolite molecular sieves were contacted, and the catalyst toxins including nitrogen compounds were removed before feeding them to the transfection reactor. wo 〇1 / 〇7383 discloses that the feed stream to the calcination zone is contacted with the spar to remove organically-bonded nitrogen. U.S. Patent No. 4,846,962 discloses contacting a solvent-extracted oil with a non-crystalline silica-alumina, or a crystalline zeolite adsorbent to remove alkaline nitrides such as NMP. The sorbent may include up to 30% by weight of water. U.S. Patent No. 5,271,835 discloses the presence of polar impurities in the C3 to C5 product fractions from the fluid catalytic cracking unit. The impurities were found to include weakly basic 0NCs in ethyl acetate. Acrylonitrile and propionitrile can also be found in the hydrocarbon stream ' as a feed to the aromatic firing process. These polar compounds are adsorbed and mother catalysts used in the aromatic tritiation process. U.S. Patent No. 98299.doc 200533651, US 6,019,887 teaches the use of cationic non-acid zeolites at temperatures not higher than 300 ° C, and U.S. Patent No. 6,107,535 teaches the use of silica to adsorb nitriles from a hydrocarbon stream at room temperature. U.S. Patent No. 2,999,861 teaches the use of X zeolites to selectively adsorb basic oNCs at -18 to 427X :, exceeding weakly basic oNCs including nitriles, nitrates and nitro compounds. U.S. Patent No. 5,744,686 and U.S. Patent No. 5,942,650 teach 'removing water from a benzene stream containing nitriles prior to removing nitriles by contacting the benzene stream with a non-acidic molecular sieve at -18 ° C to 204 ° C . US 6,617,482 B1 teaches that zeolites with higher silica are more effective when water is present. However, in the presence of water, it was confirmed that only NFM was adsorbed at room temperature; in this document, it was confirmed that the adsorption of nitriles was confirmed only in the absence of water. Low concentrations of nitriles in the range of parts per million and parts per billion will cumulatively deactivate alkylation catalysts such as coking and other inactivation mechanisms faster. Clay or resin guard beds are a cheap way to adsorb Oncs from an aromatic calcined feed stream. During the adsorption of organic nitrogen from the alkylation feed stream, coke is also formed on the adsorbent. When all the adsorption sites are occupied by 0NCsa coke, these adsorbents become ineffective. Failure of clay and resin protection beds cannot be regenerated by combustion. Protective beds containing molecular sieves can be regenerated by burning off ONCs and coke from the adsorbent. [Summary of the invention] We have found that conventional adsorbents such as clay and resinous substances are not sufficient to adsorb nitriles from hydrocarbon streams in the presence of water. We further found that at lower temperatures, acidic molecular sieve adsorbents better adsorb water and alkaline ONCs, and surpass weakly basic ONCs, such as nitriles in hydrocarbon streams. However, increasing the temperature of 98299.doc 200533651 improves the adsorption capacity of acidic molecular sieve adsorbents on water and moons. Assumption: After the acidic molecular sieve is heated up as a catalyst to hydrolyze nitrile to amine or amidine, the test amine or amidine is strongly adsorbed on the acidic molecular sieve 2 °, so 'conventional adsorbent can be prepared to adsorb part A Organic nitrogen impure substances and subacidic acid molecular sieves can be used to adsorb organic nitrogen compounds that maintain weak sensitivity, such as nitriles. Moreover, the smoke stream from the branch tower will have an appropriate water concentration and temperature to accelerate the adsorption of nitriles by the acid molecular sieve. When it fails, the molecular sieve can be regenerated. We have also found that the presence of water also reduces the build-up of anxiety on the adsorbent, thus extending the regeneration cycle. [Embodiment] The hydrocarbon feed stream of the present invention is usually a liquid, and may contain ONCs from 30 wppb to 1 mol / o, and generally ○ NCs from 〇0 w 卯 b to ⑻⑻. The present invention proves that it can adsorb ONCs at concentrations in the range of parts per million, and that we can effectively offset the concentration of ONC in the range of parts per billion on the downstream catalyst. The hydrocarbon feed stream may contain water up to and beyond saturation conditions. The hydrocarbon feed stream containing ONCs and water may be an aromatic feed stream, preferably including benzene, and suitably mainly benzene. As it flows through the adsorbent bed, the aromatic feed stream typically includes no more than 10% by weight of olefins. ONCs generally include a large proportion of basic ONCs, such as: indole, pyridine, quinoline, monoethanolamine (DEA), morpholine, including N-fluorenyl_morpholine (NFM) and N -Fluorenyl-tetrahydropyrrolidone (NMp). ONCs & may include a smaller proportion of weakly basic nitriles, such as acetonitrile, propionitrile, acrylonitrile, and mixtures thereof. The basic ONCs are well adsorbed by conventional clay or resin. 98299.doc -10- 200533651

Adhesive protection bed. The hydrocarbon feed stream is pumped into the customary impurity adsorption area by Huai Material II to adsorb sensible ONCs and other non-proprietary substances, and to provide a treated adsorption stream that lacks sensible ONCs, , Six y graded out of grade. We found that: for example, weak nitric acid-based ONCs do not adsorb well on the resins and clay adsorbents for Putian AA ~ ^ I 仃 隹 white. Nitrile

Similar to conventional adsorbent beds, it allows B d wood and can negatively affect downstream processes, such as alkylation or transalkylation reaction zones. Clay sorbents used to remove alkaline ONCs include clays provided by sudchemie, such as: sc 630 g,% 63 and preferably SC 626GS. F_24 clay provided by Filtrórcórp is also suitable. Resin adsorbents used to remove basic ONCs include resins from Amberlyst line, A-15 is preferred, and are available from Rohm & Haas Company; and such as: CT-1 75 resin supplied by Purolite International Limited. Other types of clay and resin adsorbents are suitable. Clay or resin sorbents can be used under conditions sufficient to maintain at least a portion of the aroma stream in the liquid phase. The ambient temperature is as high as 38. 〇 (100〇 卞) and pressure above atmospheric pressure up to 206 kilopascals (kPa) (30 square inches per pound) are sufficient. Clay and resin capacities are generally in the 6 and 10 weight range. /. The amine and the 2% by weight of 2NFM and NMP are relative to the weight of the adsorbent. However, under these conditions, 'clays and resins better adsorb water and NFM and NMP than nitriles. Therefore, other methods must be used to adsorb nitriles. The adsorbents of the present invention suitable for removing weakly sensible ONCs include acidic molecular sieves, such as different forms of silicoaluminophosphates and aluminophosphates, which are disclosed in US Patent No. 4,440,871, US Patent No. 4,310,440, and US Patent No. 98299.doc 200533651 4,567,029 ; And zeolite molecule I ,,, Dao Shi division. As used herein, the term "molecular sieve" is defined as a type of adsorption desiccant, which is naturally crystalline and has a crystallinity defined as microporosity or tunneling. It is distinguished from ^ -oxidized substances . The preferred species of this type of crystalline adsorbent is the aluminosilicate material, which is generally known as the jewel type. The term "fossil" generally refers to a group of naturally occurring and synthetic hydrated metal aluminosilicates, many of which are crystalline in structure. Zeolite molecular sieves in sintered form are represented by the following formula:

Me2 / n〇: a12〇3: xSi〇2: yH2〇 where Me is a cation, x has a value from 2 to infinity, n is a cation valence, and y has a value from 2 to ο. The commonly used thermal zeolites that can be used are as follows: *, oil ^, j 1 and more commonly include chabazite, also known as zeolite D; clinoptilolite, erionite, faujasite, zeolite β / Frzeite, omega X, fossil γ, _ zeolite, zeolite (m), ferrierite, mordenite, zeolite A and zeolite p. Detailed descriptions of some of the zeolites mentioned above can be found in D. W. Back, Zeolite Molecular Sieves, New York.

John Willy and his sons (J0hn Wiley and soens, New γ〇 ^), MM o in the chemical composition, crystal structure and physics such as: χ_ light powder diffraction pattern in the 'different synthesis and nature There are major differences between substances. The molecular division occurs as a finely crystalline agglomerate, or is synthesized into a fine powder, and is preferably used in the form of tablets or tablets for large-scale adsorption. The method of forming ingots is known 'It is very satisfactory, both in terms of selectivity and capacity, because the absorption characteristics of the sieve remain essentially unchanged.' Zeolite γ and zeolite χ and β zeolite with an oxide 98299.doc 200533651 aluminum or silica binder. Zeolite γ is the best. In specific embodiments, molecular sieves are usually bonded with refractory inorganic oxides. The binder can be Including oxygen charm or oxygen cutting, the former is: soil, sub-γ-emulsification, η-oxidation, and mixtures thereof are particularly preferred. The range of the molecular division ^ is from 5 to 99% by weight of adsorption tritium, and Refractory inorganic oxides can be present in a range from 1 to 95 weights. / "In one: Example: The molecular sieve can be present in an amount of at least 5. % By weight: two and the preferred amount is at least 70% by weight of the adsorbent. The molecular sieve in the adsorbent of the present invention is acidic. Use of silicon to aluminum ratio: the specification of the degree of acidity 'in one embodiment, the ratio of the material name is not less than 1GG, and in another embodiment is not more than 25. On molecular sieves The cations are not ideal. Therefore, at the zeolite / Furst m, pickling is ideal for removing metals such as sodium to show more acid sites and thus increase the adsorption capacity. The skeleton-to-binder inscription must also be avoided 'so it reduces acidity. Adding people—some amounts of cations such as earth metal and rare earth metal elements to zeolite X4Y will change the thermal and hydrothermal stability of the framework aluminum, reducing The amount of framework aluminum removed from the framework. The amount of cations added must be low enough to avoid inhibiting adsorption performance. The molecular sieve adsorbent of the present invention may have the same composition as the calcination catalyst in the downstream reactor. Or transalkylation unit. However, when the calcination catalyst is more expensive than the molecular sieve adsorbent, the composition of the calcination catalyst is preferably different from the molecular sieve. As noted, the presence of water negatively affects the room temperature at room temperature. &Amp; ^ Adsorption on the molecular sieve. What appears on the surface: It is beneficial to minimize the water in the feed to the molecular sieve protection bed 98299.doc 200533651. The water NCs compete for the adsorption site, thus reducing The ability of molecular sieves to ONCs. We determined that at lower temperatures, water adsorbs better on acidic molecular sieves than nitriles. However, we further found that in the presence of excessive concentrations of water, acidic molecular sieves adsorbed at higher temperatures More concentrated nitriles. Although we do not want to be limited by any special reason, we are not aware that nitriles are not sufficiently susceptible to adsorption on acidic molecular sieve adsorbents. Then, in the presence of water, nitriles are acidic. The molecular sieves are catalytically hydrolyzed into ammonium amines or amines. The basic ammonium amines or amines are then adsorbed onto the acidic molecular sieve. The contaminated hydrocarbon feed stream to purify the waxes must be in the presence of water 3. The adsorption area flowing through the acidic molecular sieve under elevated temperature is at least 12CTC and not higher than 30 ° C in one specific embodiment. In another specific embodiment, the range is greater than 125C and not higher than 300C. (And, in another specific embodiment, the range is greater than 150 ° C and not higher than 2000. The pressure in the adsorbent bed must be between 34.5 kPa and 4136 kPa (Absolute) (5 to 600 square inches per pound). Before regeneration is required, the ONC load on the molecular sieve adsorbent reaches from 0.6 to 10% by weight. On the clay adsorbent, 0NC The load is from 1.5 to 60% by weight, and the 0NC load on the resin adsorbent is twice that of clay. Because the resin or clay adsorbent has a larger adsorption capacity for ONCs and is cheaper, it is delivered to Before the acidic molecular sieve protection bed removes nitriles, impure hydrocarbon streams flow through the conventional clay or resin protection bed to remove alkaline ONCs. However, the acidic molecular sieve protection bed will adsorb alkaline ONCs. Adsorbent bed remains. It is preferred that the device has an acidic molecular sieve adsorbent bed that circulates downstream with the conventional adsorbent bed 98299.doc -14-200533651. Therefore, at least a portion of the effluent from the conventional adsorbent bed must eventually be fed to the acidic molecular adsorbent bed. Furthermore, because the temperature of the outflow from the conventional adsorbent bed can be the ambient temperature, the heat exchanger can be placed downstream to communicate with the conventional adsorbent bed and upstream to communicate with the thermal adsorbent bed to adjust the temperature suitable for the thermal adsorbent bed. temperature. Thus, at least part of the effluent flow from the ㈣ agent bed will be heated or cooled in the heat exchanger, and at least part of the effluent flow from the heat exchanger will be entrained into the thermal adsorbent bed. In one particular embodiment, all of the institutionalized matrix stream must be denitrified on a thermal adsorbent bed before it is fed into the alkylation and / or transalkylation reaction zone. When on a molecular sieve guard bed, the water concentration in the smoke feed stream must be between 20 wPPm and 500 wppm, and preferably between 50 and 150 WPPm. In one implementation, the water concentration must be related to the stoichiometry of the conversion of wax to acid amines or amines. We have also found that the presence of water in the molecular tritium bed reduces the formation of coke on the adsorbent at elevated temperatures. The accumulation of coke at the acid position of the molecular sieve acts as a barrier to the adsorption of ONCs 'causing a shorter cycle between regenerations'. However, by reducing coke formation at the acid position, the molecular sieve protection bed can be maintained longer after regeneration and Maximum adsorption capacity is maintained during multi-cycle operation, since each regeneration cycle requires much less stringency. When it fails, the conventional clay or silk guard beds cannot be regenerated. However, the failed clay or m must be discarded. The ineffective molecule Xue of the present invention can be regenerated. The molecular sieve protection bed may include—or multiple fixed bed molecular sieves. When the capacity of the molecular sieve adsorption bed in operation is reached, that is, preferably before the majority of the ONCs pass through the molecular sieve adsorption bed in operation, the feed stream is directed to a spare molecular sieve adsorption bed in the adsorption zone. The former then puts the adsorbent bed into operation to drain the contents through the fractionation zone. Otherwise, the process is stopped during regeneration of the adsorption bed. The adsorbent bed can be regenerated by a hot natural gas stream, or burned ONCs from molecular sieves by sintering, or by any other conventional method. The regenerated adsorbent bed is then placed on standby until it reaches the capacity of the adsorbent bed in production. In the selective alkylation of aromatics with refined olefin alkylating agents and acidic catalysts, olefins can contain from 2 to at least 20 carbon atoms, and can be knife or linear olefins, terminal or internal olefins. . Therefore, the nature of the olefin is not particularly important. The common reaction of the hospitalization reaction is that the reaction is performed under the condition of at least liquid phase, which is a standard that can be easily reached for low-carbon members by adjusting the reaction time and again. Among the low-carbon dilute hydrocarbons, ethylene and propylene are the most important representatives. The olefin feed stream comprising the burner may include ethylene and / or propylene. The olefin-containing feed stream including propylene will be at least 65% by weight pure, and some of the weight% feed will exceed M% by weight. Ethylene feed-generally more than 99% by weight is pure. Of the remaining thin fumes though, detergent range olefins and the like are of particular interest. This class contains = ° :. The linear olefins are composed of linear thin smoke, which have internal or terminal, main 223, and 8 to 16 carbon atoms. The linear olefins are especially used as enc olefins, and those containing from 10 to 14 carbon atoms are special仏 Thin smoke as a cleaning agent. , Serving is provided in the transfusing reaction area. -1 ° / Cyclosylbenzene group ... e, monoethylbenzyl, triethylbenzene, and diisopropyl clay: important examples of alkylbenzene, which can provide such a calcining agent. The present invention is by far the most important representative of aromatic compounds that can be burned, which can be used as the burning matrix in the implementation of the invention of 98299.doc 200533651. The aromatic feed stream can contain from 5 to 9 "mole% of benzene 'and can be a recycle stream from the production of styrene monomer. More generally, aromatic compounds can be selected from free benzene, amidine, lean, The group consisting of phenanthrene and its substituted derivatives. The most important type of substituents found on aromatic compounds are radicals containing carbon atoms. Another important substituent is via radicals, Its alkyl group also contains a group of oxygen radicals from U20 carbon atoms. Among them, the substituent is alkyl or alkoxy, and the phenyl group can be substituted on the stoneworm chain. Although unsubstituted, disubstituted and Mono-substituted benzene, naphthalene, phen, and phenanthrene are the most commonly used in the practice of the present invention, and poly-substituted aromatics can also be used. In addition to those described above, examples of suitable alkylatable aromatic compounds include biphenyl, toluene, diphenyl Toluene, ethylbenzene, propylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, etc. A wide variety of catalysts can be used to burn the reaction zone. Suitable catalysts for this reaction zone The media can include any Catalyst. Preferably, a large amount of water can be tolerated or required in the presence of a coin catalyst. A large amount of water is preferably meant to be at least 50 wppm in the reactants entering the burning zone. The calcination reaction area may have a water content as low as 2 wPpm, to more than 200 wppm, and as high as noodles or more, the Chevrolet catalyst of the present invention is a zeolite catalyst. The catalyst is used in combination with a resistant = inorganic oxide binder. The preferred binder is oxidized or emulsified hard. Suitable zeolites include zeolite β, MM], ㈣ 2 MCM_36, MCM-49, and batch 156. Zeolite β is described in Wu Guo patent US 5,723,71. The preferred chemical catalyst is a ¥ fossil with an oxidation 98299.doc 200533651 or a silica adhesive, or an oxide with a silica or a silica adhesive. Beta zeolite. Zeolite is present in an amount of at least 50% by weight of the catalyst, and more preferably in an amount of at least 7 (%) by weight of the catalyst. The special conditions under which the calcination reaction proceeds depend on the aromatic being present: Daggers and olefins, because the reaction proceeds under the condition that at least part of the liquid phase The force is adjusted to maintain the dilute hydrocarbon at least partially in the liquid phase. For high-carbon dilute hydrocarbons, the reaction can be carried out under autogenous pressure. The pressure can be between 101 kPa and 1 3 1 72 kPa. Variations in a wide range. For pragmatic situations, the pressure is generally between 1379 kilopascals and 6985 kilopascals (per square to 10000 squares, but usually between 2069 and 4137 kilobars). Range between 300 to _ square pairs per stone. But we stress again: pressure is not a critical variable and only ^ is required to maintain at least part of the liquid phase condition. Representative tritiated temperatures include Fei Tritiated benzenes range between 170 C and 250 C, and propylene alkylated benzenes range between 90 ° and _. The temperature range suitable for the calcination of the alkylizable aromatic compounds of the present invention in the range of C2 to Cm is between 60 ° C and 400 ° C. The most common temperature range is between 90 ° and 250 °: . The reactants hang through the alkylation zone at a mass flow rate sufficient to produce a liquid hourly space velocity from 02 to 50 hours, and particularly from 05 to 10 hours4. ^ The ratio of alkylable aromatic compounds to olefins used in the process of the present invention will depend on the degree of selective alkylation desired and the relative costs of the aromatic and olefin components in the reaction mixture. For alkylating benzene with propylene, the ratio of stupid to olefin can be as low as 15 and as high as 100, and a ratio of up to 8.0 is preferred. When benzene is alkylated with ethylene, the benzene-to-olefin ratio is preferably between 98299.doc -18- 200533651 2: 1 and 8: 1. For cleaners ranging from C6 to Cm, benzene-to-olefin ratios between 5: 1 and 30: 1 are usually sufficient to ensure the desired burn selectivity ', while at 8: 1 and 2G: 1 The range is even higher. In the production of cumene with a benzene alkylation matrix and a propylene alkylating agent, propylene-containing streams also typically include propane. The propylene stream may contain from 0 to 50% by weight propane, and in general the propylene stream may contain from 5 to 35% by weight propane. The alkylation reaction zone typically provides a wide variety of unwanted by-products. For example, • Ethylene is burnt to produce ethylbenzene. In addition to other ethylene condensation products, di- and triethylbenzene can also be produced in this reaction zone. Similarly, benzene is alkylated with propylene to produce cumene. In addition to still more condensation products, this reaction zone $ can produce di- and tricumyl. These multi-burned aromatics in the tritiation reactor are exposed to additional aromatic groups f to generate additional monomers: The zeolite catalyst is used in the trans-sintering reaction zone of the benminite. The zeolite is present in an amount of at least 50% by weight of the catalyst, and a preferred amount is at least 90% by weight of the catalyst. In most cases, the zeolite catalyst further includes an inorganic oxide binder. The preferred inorganic oxide for the transalkylation catalyst is alumina, with γ-alumina, η-alumina and mixtures thereof being particularly preferred. The zeolite is present in the range of 5 to 99% by weight of the catalyst, and the refractory inorganic oxide binder may be present in the range of 1 to 95% by weight. Preferred transalkylation catalysts are zeolite gamma with alumina or silica binder, or beta zeolite with alumina or silica binder. It is not necessary to use the same catalyst for the alkylation reaction zone and the transalkylation reaction zone. This process is used in the alkylation reaction zone and in any row of the transalkylation reaction 98299.doc -19- 200533651. However, it has been found that when used in the tritiation reaction zone and the transfiring reaction zone, or both, the β zeolite or high zeolite type zeolite which is contained in the alumina binder performs well. Therefore, in a specific embodiment of the present invention, 'in the cumene content, the same catalyst · beta zeolite is used in the two reaction regions. On the contrary, in the case of ethylbenzene, it is preferable to use beta zeolite and rhenium-type zeolite in the alkylation and transalkylation reaction regions, respectively. In addition, transalkylation reaction 'occurs in the alkylation trans-C region and a tritiated reaction is generated in the transalkylation reaction region, and the two regions may be referred to as alkylation regions. It may be desirable to use a first bed of an alkylation zone or a transalkylation zone that uses an acidic molecular sieve catalyst as the adsorbent zone to remove nitriles. In this case, the sorbent and catalyst must be spaced apart. The alkylating agent must bypass the adsorption zone and be transported into the interbed space to be mixed with the denitrified alkylating matrix present in the adsorption zone. However, it is preferable to include a heat adsorption region and an alkylation region in separate containers. The transalkylation reaction can be performed under a wide range of operating conditions including temperatures from 100 C to 390 ° C (212 ° F to 734 ° F) and pressures ranging from 101 to 13171 kilobasca (14 per pound) 7 to 1910 square inches). Furthermore, the pressure pump is remotely selected so that the reactants are maintained in the liquid phase. Therefore, the preferred pressure range in the transalkylation reaction zone is from 1013 to 5066 kilopascals (147 to 734 square inches per pound). The hourly space velocity of the liquid from 0.2 to 50 hours-is ideal for the transalkylation reaction zone, and the LHSV is preferably from 0.5 to 50 hours-1. The transfiring and firing reaction zones may be operated and arranged in any way, which provides the desired operating temperature and number of contact stages. 98299.doc -20- 200533651 for the heavy contact stage in the calcination area, which is used for tadpoles in the calcination zone to add reactants to the calcination catalyst.

Multiple beds to provide cooling. Multiple injection of reactants acts as a cooling stage between the catalyst bed and provides temperature control. Therefore, the catalyst is arranged in a multiple bed to allow the bed to be injected with a calcining agent. Separate firing catalyst beds can be arranged in a single container or multiple containers. The present invention can use a conventional parallel arrangement for the alkylation zone and the trans-sintering zone, in which the feed stream is sent to each reaction zone independently, and the effluent is recovered separately. In addition, the reaction zone can have a series of flow arrangements for the effluent stream from the transamination zone to the calcination zone with additional benzene, or vice versa. In the calcination zone, a large excess of benzene can pass through a series of alkylation catalyst beds, with an intermediate stage injection of the calcining agent and any additional amounts of benzene. The circulation of the effluent stream from the calcination reactor can also be advantageously used to stop the respective catalyst beds to further improve the temperature control 'without the need for additional consumption of fresh benzene. In a series of flow =, a general vessel may include a trans-sintering reaction zone and one or more anti-shoaling zones. For very large units, the individual containers used for the transfer catalyst bed and one or more alkylation catalyst beds are more advantageous.

Individual areas are used to recover the alkylation products. In the separation zone, at least the top condensers closed to leave can be used to separate the ^ I and " smelled aromatic hydrocarbon condensate from the overhead stream back to the column for reflux. From the top: It is difficult to remove water because of the high solubility of water in benzene. However, some water in benzene * accelerates the removal of nitriles. The top condenser of the benzene column can be operated to reduce water concentration to wppm. The intermediate stream from the depropanizer column can be supplied with a benzene stream having a water concentration of 50 to 150 wPpm. The detailed description of specific embodiments of the method and device in January will not be presented with reference to the accompanying drawings. This illustration represents a view of a specific embodiment of the present invention, and is 98299.doc -21-200533651 and is not intended to be essential in the general broad scope of the present invention and the limitations of the claimed items. Some various Attachments, including valves, pumps, separators, receivers, heat exchangers, etc., are excluded from the picture. Only those containers required for a clear and complete understanding of the method and apparatus of the present invention are described. In all cases, the process is a continuous process. Figure 1 illustrates a specific embodiment of the present invention for the production of ethylbenzene. The ethylene-containing stream enters the process in line 14 and is injected into the first and second alkylation reactors 20, 30, respectively. Although the transalkylation reaction occurs in the alkylation reactors 20 and 30, the alkylation reaction is the main, and the alkylation reactor is shown as an upstream reactor, but a downstream reactor is also suitable. Ethylene is injected into the calcination reactors 20 and 30 in lines 14a-f, and before entering the catalyst beds 20d_f and 30d-f, it goes to the bed front spaces 20a_c and 30a-c. The catalyst beds 20d_f and 30d-f contain alkylation catalysts to alkylate benzene and ethylene to produce ethylbenzene. Benzene on line 10 is fed into the first alkylation reactor 20, where it is initially mixed with ethylene from line 14a in the bed headspace 20a and enters the catalyst bed 20d. The outflow from the catalyst bed 20d is mixed with fresh ethylene from the line 14b in the bed front space 20b and enters the catalyst bed 20e. The process is repeated with the number of beds in the first alkylation reactor 20. Although three catalyst beds are displayed in the alkylation reactors 20, 30, more or less may be appropriate. The intermediate alkylation effluent from the first alkylation reactor 20 is transported to the second in line 8 :): the completion reactor 30. Before it is transported to the bed front space 30a, the heat exchanger 22 cools the effluent in line 18 to the desired firing temperature. Ethylene from the injection bed headspace 30a from line 14d is mixed with the intermediate alkylation effluent stream from line 18 and enters the catalyst bed 98299.doc -22-200533651 30d. The same process was repeated for the catalyst bed 30e & 30f, and the alkylation reactor effluent from the second alkylation reactor 30 was transported to the benzene 40 " Hollowerization reaction in line 32 The outflow can be depressurized by a pressure control valve not shown, and can be heated by a heater or heat exchanger, or both, which are not shown. Additionally ' more or less alkylation reactors may be suitable. If the alkylation reactors 20 and 30 and the transalkylation reactor 50 are operated in parallel as shown in Fig. I, benzene from the line 10 is routed to the transfaction reaction state 50 via the line 52. Line 54 carries polyethylbenzene (PEB) overhead diethylbenzene (DEB) and triethylbenzene (teb) from the top of PEB column 90, and is mixed with the bulk in line 52 to provide a transalkylation feed line 58. The transalkylation reactor 刈 includes three catalyst beds 50a-50c containing a transalkylation catalyst. More or less catalyst beds can be used in the transalkylation reactor 50. The transalkylation catalyst promotes the transalkylation reaction, in which ethyl groups from DEB and TEB are transalkylated with benzene to produce ethylbenzene. As a result, the official line 56 contains a greater concentration of ethylbenzene and a lower concentration of DEB and TEB than the transalkylation feed line 58. As shown in FIG. 1, the alkylation and transalkylation reactors are parallel, and three different materials are fed to the benzene column 40. The alkylation reactor effluent stream in line 32 and the trans-alkylation effluent stream in line 56 are fed with benzene, ethylbenzene, butylene RE and heavier PEBs into benzene column 40. Fresh feed benzene in line 12 is passed through a conventional adsorbent container stock containing a bed of clay or resin adsorbent 46 to adsorb impurities. The line contains 48 basic NCs from the benzene stream to purify the benzene to Stupid i go 40. The purified benzene stream typically contains between 400 and 800 milliseconds of " the sigma 40 is fed off into at least two streams. The top of the benzene column containing benzene *, the two leaves the benzene tower from the official line 62, and performs a condenser 64, in which the temperature is 98299.doc -23 · 200533651, but the temperature is between 120 ° C and 170 ° C. The condensing top enters the receiver 66, which includes traps for dispersing insoluble or free water in line 66a, and light gas in line 66b if necessary. The top hydrocarbon stream contaminated with ONCs including nitriles in line 68 is transported to the thermal adsorbent container 70, while a portion of the top hydrocarbon stream is returned to the benzene column 40. The top hydrocarbon stream includes 50 to 500 wppm water. The thermal sorbent container 70 contains a thermal sorbent molecular sieve bed 72 which is an acidic molecular sieve, which will adsorb ONCs including nitriles under appropriate conditions. The temperature and water concentration of the top hydrocarbon stream in line 68 are well adapted to selectively adsorb nitriles from the hydrocarbon stream with acid molecular sieves. Therefore, the denitrided benzene stream in line 10 does not actually contain ONCs, which is no more than 30 wppb. The bottom stream of the benzene column, which contains the product ethylbenzene and by-products including PEBs, leaves the column in line 74 and enters the ethylbenzene column 80. The ethylbenzene column 80 separates the benzene column bottoms stream from line 74 into two streams by distillation. The ethylbenzene column overhead stream containing the product ethylbenzene leaves the ethylbenzene column 80 in line 82 and is recovered from the process. The bottom stream of ethylbenzene tower contains by-products PEBs, generally including DEBs, TEBs and heavier PEBs, such as: butylbenzenes, dibutylbenzenes, tributylbenzenes, ethylbutylbenzenes, diethyl Butylbenzenes and diphenylethane. The ethylbenzene column bottoms leave the ethylbenzene column 80 in line 84 and pass through the PEB column 90. PEB column 90 separates the ethylbenzene column bottoms stream in line 84 into two streams. The underflow of the PEB tower containing PEBs heavier than TEB left in line 92 from the bottom of the PEB tower 90 and was rejected from the process. The top stream of the PEB column containing DEBs and TEBs exits from the PEB column 90 in line 54 and is recovered as previously described, mixed with the 98299.doc -24-200533651 feed in line 52 to the transalkylation reactor 50 . In the picture! The specific example in Figure 2 uses two sorbent beds that cooperatively remove ONCs from the calcined matrix feed when all of the textured matrix may be contaminated with ONCs. The resin or clay adsorbent ⑽ removes a large amount of ο ·, and at the same time, the thermal sorbent molecular sieve bed 72 adsorbs the remaining fluorene including nitriles, which poisons the tritiated and burnt catalyst. Figure 2 shows a method and apparatus which can be used with advantage when recovering benzene from another source such as: styrene monomer units. The method and apparatus are used to make total benzene for ethylbenzene. And recycled benzene from other sources may be contaminated with ONCs. All reference numerals of the components marked in Figure 2 correspond to the figure! Similar components in, but with different types are marked with a single point symbol (,). Otherwise, the same reference numerals are assigned to corresponding components having the same type in FIGS. I and 2. In addition, although ㈣2 shows that the calcination reactor and the transalkylation reactor are parallel, they can be operated in series. Fresh feed benzene in the official line 12 'flows through a conventional adsorbent container 44 containing a resin or clay adsorbent bed 4 6 to adsorb impurities including ◦ n cs from the benzene stream. Nitriles are expected in the fresh feed benzene in line 12 ,. The purified benzene stream typically contains 400 to 800 wppm water. Line 48, which carries the purified benzene stream ' combined with the benzene tower top stream in line 68, Phase I contains benzene, another source of gambling, and is carried in line 8 to the thermal adsorbent container. The benzene stream in line 8 is recovered from the styrene monomer unit and may contain water between 50 and 800 claws, and is generally water saturated. The thermal adsorbent container 70 contains an adsorption bed 72 of an acidic molecular sieve, which absorbs water under appropriate conditions and needs to be injected with ONCs including nitriles. If the water concentration is lower than 50 wppm 98299.doc -25- 200533651 into stupid stream. If the water concentration is higher than 50 Wppm, it is advantageous to dry the benzene stream. If the temperature of the benzene stream in line 8 is not at least 20 ° C, and preferably higher than us and not higher than 300 ° C, it must be heated or cooled to an appropriate temperature. This temperature range and water concentration are well suited for selective adsorption of nitriles from hydrocarbon streams, acidic molecular sieves, and basic NCs. Therefore, the denitrified benzene stream in line 32 does not actually contain 0 NCs to a detection amount of 30 wppb, is mixed with the purified benzene stream in line 48 ', and the top of the benzene column in line 68 The streams are mixed to provide a nitrogen-free benzene stream in line 10 ,. The benzene stream in the official line 10 'is sent to the alkylation reactors 20, 30 and is sent to the transalkylation reactor 50 through the parallel official line 52'. At line 10, the benzene in is transported to the alkylation reactors 20, 30 and reacts with the ethylene supplied from line 14 on a suitable catalyst, as explained with respect to Figure 丨. The alkylated effluent in line 32 is sent to a benzene column 40. The DEB and TEB from the overhead stream of PEB in line 54 are mixed with the benzene stream in line 52, to provide a transalkylation feed stream in line 58 which is sent to the transalkylation reactor 5 〇 中. The reaction of DEB and TEB with benzene in reactor 50 produces DEB and TEB with increased concentrations of ethylbenzene and the transalkylation effluent stream in line 56 relative to the transalkylation feed stream in line " Reduce the concentration. The transboiled effluent in line 56 is transported to the benzene column 40. The tower 40 separates the feed into at least two streams. The benzene-containing benzene column overhead stream leaves the benzene column via line 62, And enters the condenser 64, where it cools to a temperature between 120 ° C and 170 ° C. The condensation top enters the receiver 66, which is used to disperse the insoluble water in the line 66a, and if necessary The light gas trap in line 66b. In line 68, it contains most of the stupid 98299.doc -26- 200533651 top hydrocarbon stream, which was recovered to line 10 | A portion was refluxed to benzene column 4. The benzene tower bottom stream containing the product ethylbenzene and by-products including pEBs left the benzene tower in line 74 and entered the ethyl main column 80.

The ethylbenzene column 80 separates the bottom stream of the benzene column into an ethylbenzene i-th column top stream containing product ethylbenzene in line 82 and an ethylbenzene i-th column bottom stream containing by-products in line 84, which Via Peb Tower 90. The pEB column separates the ethylbenzene column bottom stream into pEB column bottom stream in line 92, which is pEBs heavier than TEβ, and PEB column overhead stream in line 54, which are recovered as described above for transalkylation. Reactor 50. Fig. 3 shows the transalkylation reactor 50 and the alkylation reactors 20 and 30, which are operated similarly to Fig. 1. All the reference numerals of the components marked in FIG. 3 correspond to the ode-like components in FIG. 1, but the different types are marked with a double comma (,,). Otherwise, the same reference numerals are assigned to corresponding components having the same type in Figs. I and 3. The transalkylation reactor effluent stream from the transalkylation reactor 50 may be connected in series to the alkylation reactor 20 via line 56 "instead of being transported to the reactor 40. In line 32";): Finishing The reactor effluent stream and the purified benzene stream in line 48 were routed to a benzene column 40. The benzene stream from the top stream of the benzene tower in line 68 is denitrified on the thermal adsorbent molecular sieve bed 72 in the thermal adsorbent container 70. The denitrification stream in line 10 is diverted to the transalkylation feed in line 52, and before entering the transalkylation reactor 50 in line 58, and from line 54 from the PEB column 90 PEB tower tower top stream mixed. The transalkylation effluent in line 56 "and the remaining deazabenzene / melon in line 10 & and enter the calcination reactor, as described in the drawing 98299.doc -27- 200533651 Figure 4 depicts the process and equipment used to produce cumene according to the present invention. The propylene stream in line 100 is mixed with the benzene stream in line 102, and line 101 introduces the benzene and propylene mixture to The first catalyst bed 122a in the calcination reactor 120. The alkylation reactor 120 is shown as a downflow reaction state, but a sloping upflow reactor is also appropriate. The catalyst bed 1 22a is used to burn propylene The sintering catalyst that is isopropyl is discharged, and the effluent from the catalyst bed 122 & enters the bed space 124a. The recovered alkylation effluent k from the line 106 is cooled by the hot parent converter 108. And the distribution line 106a_e and the feed inlet lines 104a-e are recovered into the alkylation reactor 120. The propylene in the official line 104 from the diverting line 100 is distributed to the feed inlet line 1. 〇4a-e, where they are respectively mixed with recovered alkylation effluent streams from distribution lines 106a-e The recovered alkylated effluent stream and propylene mixture in the feed inlet lines 104a-e are transported to the respective interbed spaces 124a-e, where they are separately associated with those from the Lishu catalyst beds 122a-e. The effluent streams are mixed and individually enter the subsequent catalyst beds 122b-f. The tritiated effluent stream leaves the catalyst bed 122f in line 107. A portion of the alkylated effluent stream is recovered to the alkylation reactor via line 106. At 12 o’clock, the other part of the same line was routed to the depropanizer tower 30 in line i 26. The fresh feed benzene in the squall line 110 was placed in the resin or clay adsorbent bed 114. The conventional adsorbent container U2 is purified to remove alkaline ONCs. A purified benzene stream containing 400 to 800 wppm water is transported to the depropane tower 130 via the line ιΐ6. The depropane tower 13 〇 An intermediate stream containing benzene and 50 to 150 wPPm water in line 132 is provided, and the temperature is up to I20 C, and preferably greater than 125 ° C and not more than 170 ° C. These properties are 99299.doc 200533651 can be adjusted to prepare a benzene stream in line 132 to adsorb nitriles. In a specific embodiment, in line 132 The temperature of the intermediate stream is a result of the heat generated in the depropane column 130 from the reboiler (not shown), and the heat from the depropane column 130 to a condenser (not shown) which is a general device in the distillation column (Shown) removed. If water is insufficient in the benzene stream due to feed composition or other conditions, water can be injected into line 132. In addition, although the intermediate stream in line 132 can be pulled out sideways, the dividing wall column It can be used to provide a better intermediate cut. Depropanizer column 130 rejects propane and excess water in line 134 at the top of the column. Heavier hydrocarbons than propane are removed via line US, earthen bottom stream, and transported to benzene column 140. After it is mixed with the transalkylated effluent stream in line 152, the benzene column 14o receives the feed in the official line 136 from the bottom of the depropanizer column 13o. The benzene column 140 generates a benzene column top stream containing benzene in line 142 and a benzene column bottom stream containing ethylbenzene and pEBs in line 144. The top stream of the benzene tower in line M] may have a water concentration of 50 to 15 wppm and a temperature of at least 120 ° C, and preferably more than 125 t, and not more than 170. The depropanizer intermediate stream in line n] has similar properties and is combined with stream 42 and is conveyed to the thermal adsorbent container 16 by line 161. The thermal sorbent capacity of 1 60 contains an acidic molecular sieve adsorption bed for removal, including nitriles in line 161 from the mixed benzene stream. The denitrified benzene outflow in line 164 is conveyed to the alkylation reactor 120 through the line 102 and to the trans-boiler reactor 15 through the line 166. Benzene stream in line 166: Intermediate stream from distillate column 190 and diisopropylbenzene (dib) in official line 168 are mixed. The mixture of benzene and mB in line 154 is transported to the transalkylation 98299.doc -29- 200533651 to a reaction of 150. DIB and benzene are fired on a transalkylation catalyst bed 156 in a transalkylation reactor 15 to produce cumene. The reburning stage in line 152 is hungry, which has a higher concentration of cumene and a lower degree of benzene and DIB than in official line 54. The top stream of the benzene tower in & line 144 is transported to the cumene tower 80. The isopropylbenzene column 180 provides an cumene overhead stream containing the product cumene, which is recovered into line 182. The top stream of the cumene column in line 184 contains heavier hydrocarbons than cumene and is transported to a weight column 190. The weight column 190 produces a DIB-containing intermediate stream in line 168. The lighter material in the top stream of the heavy tower is removed in line 192, and the bottom stream of the heavy tower is removed in line 194. FIG. 5 shows a flow similar to that of FIG. 4 except that the fresh benzene stream is purified in a conventional adsorbent container 112 containing a resin or 4 occupant and a bed 114, and then before entering the depropanizer column 130, in the heat The adsorbent container 160 is denitrified. All the reference numerals of the components marked in FIG. 5 correspond to the canine-like components' in FIG. 4 but have different types and are indicated by a single comma (,). Otherwise, the same reference numerals are assigned to corresponding components having the same type in FIGS. 4 and 5. Line 10, passing fresh feed benzene to the conventional adsorbent container U2, 'line 116', transports purified benzene from the adsorbent container U2 to a thermal adsorbent container 60 containing an acidic molecular sieve adsorption bed 1 62, and the line 64. Feed denitrogenated benzene to a depropanizer column 30. The intermediate stream from the depropanizer column 30, in line 132 ′, is mixed with the benzene from the top stream of benzene column, in line 142 of benzene column 140, and sent to the alkyl group in line 102. Chemical reactor 1 20 ° Otherwise, the flow in FIG. 5 operates roughly as in FIG. 4. 98299.doc -30- 200533651 Fig. 6 shows a flow similar to that of Fig. 5, except that the thermal adsorbent bed i62, is provided to the conversion reactor. All reference numerals of the components marked in Fig. 6 correspond to similar components in Fig. 4, but with different types, they are indicated by double comma r). Otherwise, the same reference numerals are assigned to corresponding elements having the same type in FIGS. 4 and 6. Benzene in line 110 is purified with basic NCs in a conventional adsorbent container 112 containing a resin or clay adsorbent bed 114. Line 116 is fed with purified benzene and the alkylation effluent from alkylation reactor 120 in line 126 flows to depropanizer column 13Q. The deprotonated intermediate stream in the squall line 1 3 2 is transported and mixed with benzene from the overhead stream of the benzata, diverted via line 166 "to line 142, and fed to the transalkylation reactor 150. ". The control valve 188 regulates how much dib from the heavy column 190, the heavy intermediate flow in line 168, is mixed with diverting to the top stream of this column in line 1 66, and bypasses line 154 to a certain extent, 186. The transalkylation reactor 15 ″ includes a sacrificial thermal adsorbent bed 162 ″ of an acidic molecular sieve catalyst for adsorbing ONCs including nitriles. The denitrified feed from the sacrificial thermal adsorbent bed 162 "is mixed in the interbed space 157 'with the DIB from the bypass line 186 and enters the dealkylation catalyst bed 156". DIB and benzene are transalkylated on the transalkylation catalyst bed 156 ", resulting in the trans-baking effluent stream of isopropyl in line 152, which has a higher concentration than cumene in line 1 $ 4 and Lower concentrations of benzene and DIB. The transboiler effluent stream in line 52 is mixed with the depropanizer bottoms stream in line 36 and fed to the benzene column 140. In the fresh benzene stream in line 110 98299.doc 31 200533651 which is not adsorbed by the conventional adsorbent container 11 2 and is not rejected in the overhead stream of the depropane column in line 134. All nitriles will be present in the intermediate stream in line 132 ". Nitriles-free species will be present in the depropanizer bottoms stream in line 136. In line 110, all nitriles from the fresh feed stupid stream that survive the process will be in line = 2, '. The flow in line 166 "only goes in the direction of the arrow" A ". Therefore, all nitriles in line 132 "will be directed to the sacrificial thermal sorbent bed 162 ,, to remove nitriles. Nitrile-free travels from line 166, to line ι02 " because there is no The nitriles will be in the intermediate flow in line 168. Preferably, all the heavy doors will bypass the sacrificial thermal adsorbent bed 162 via the bypass line 86. The flow in FIG. 7 is different from that in The flow in Figure 6 where the depropane in line 2 | § Intermediate stream combined with the benzene column overhead stream from line 142 is formed in line 1G2, benzene feed stream, and sacrificial thermal adsorption The agent bed 162 "is a guide bed for the calcination reactor 12". All the reference numerals of the components marked in Fig. 7 correspond to similar components in Fig. 4, but with different types of evils, they are marked with two commas. Otherwise, the same reference numerals are designated as corresponding elements having the same type in FIGS. 4 and 7. The benzene feed stream in line 102 '' 'only flows in the direction of the arrow "β". As shown in the process of Figure 6' in line 11 ', the benzene stream is from a fresh feed benzene stream and is alive in the process: with nitrile Will be in line 132 .... All nitriles in line 132 ... will be directed to the sacrificial thermal adsorbent bed 162 ,, in the calcination reactor 120 ... to remove wax. From sacrificial heat absorption The denitrified benzene effluent from the bed 162 ,, and enters the bed interlayer space 124a '' ', the soybean blood in the basin, and the propylene distributed from the U, 104, and U pipelines. Mixing 5. Cooling and calcination effluent from pipe, line 106, ... through distribution line 98299.doc -32 · 200533651

1〇6π-6 · ′ | was recovered to the calcination reactor 120, and, to the feed inlet line 104b-e. The propylene in the official line 104 is distributed to the feed inlet lines 104b-e, where they are respectively mixed with the recovered alkylation effluent stream from the distribution line 〇06b ", _e | ". The recovered alkylated effluent stream and the propylene mixture in the feed inlet line 104b ,, _en, are transported to the respective bed layer = bay 124b-e, where they are separately associated with the catalyst bed from the aforementioned catalyst bed. 122b ,,, _ e ,,, and the outflows are mixed and enter the subsequent catalyst beds 122c ", _ f, " respectively. The alkylation effluent leaves the last catalyst bed 122fn in line 107. A part of the alkylation effluent is recovered to the alkylation reactor 120 through the line 106 ", while another part is routed to the depropanizer column 13 through the line 126.

Figure 8 depicts the flow of combining similar elements in Figures 6 and 7, using two sacrificial thermal adsorbent beds. All reference numerals of the components marked in FIG. 8 correspond to similar components in FIG. 4, but they have different types and are indicated by a ten character (t). Otherwise, the same reference numerals are assigned to corresponding elements having the same pattern in Figs. A sacrificial heat absorption bed_ provided in the transalkylation reactor 150t, as described with respect to FIG. 6, and a second sacrificial heat sorbent bed 16 沘 is provided in the alkylation reactor 12 inches, As described with respect to FIG. 7. The depropanizer column intermediate stream in line 132 卞 is divided into two streams / J, the transalkylated benzene feed stream carried in LS line 1 33, and the top stream from the benzene tower diverted via line 166t in line 142. Mix and feed to the tritiation reaction 150 via line 54t. The sacrificial thermal sorbent bed 162a of the acidic molecular sieve catalyst adsorbs NCs from the feed stream, including nitriles. The denitrified feed from the sacrificial thermal adsorbent bed 162a is mixed with the DIB from the bypass line 186 in the interbed space 157 and enters the transalkylation catalyst bed 98299.doc -33- 200533651 1 56f. DIB and benzene were trans-fired on a trans-fired catalyst bed 156 * f, which produced isopropylbenzene. The transboiled effluent in line 1 52 has a greater concentration of cumene and a lower concentration of benzene and DIB than in line 1 54 卞. The diverted outflow in line 152 is mixed with the depropanizer column bottom line in line 136 and fed to benzene column 140. The second stream in line 135, which is derived from the depropanizer column intermediate stream in line 132t, combines the benzene column overhead stream from line 142 to form the benzene feed stream in line 10 and is transported to the second The sacrificial thermal adsorbent bed is directed to the sintering reactor 1220. The denitrogenated benzene effluent from the sacrificial thermal adsorbent bed is entered into the bed interlayer space 124a, where it is mixed with propylene distributed by the line 104t. The alkylation in the alkylation reactor is performed as explained with respect to FIG. The effluent stream from the calcination reactor is carried in line 126 to the stripper column UG. Because in the pipeline i6q, the benzene flow turns only in the direction of the arrow "A", and in the pipeline 10, the benzene flow = the flow only flows in the direction of the arrow " B ". In line 110, all the nitriles from the fresh feedstock that survive the process will be in line MM. Because all of the nitriles in line 1 32 卞 will be directed to the sacrificial thermal adsorbent bed 162a in the trans-sintering reactor or the sacrificial heat and additive bed 162b in the calcining reactor 120 ° to remove all The remaining GNCs include nitriles as low as 30 wPPb. Fig. 9 depicts another process for producing cumene according to the present invention without using a depropanizer column. All the reference numerals of the components marked in FIG. 9 correspond to similar components in FIG. 4, but with different types, they are indicated by double ten characters. Otherwise, the same reference numerals are assigned to corresponding elements having the same type as 98299.doc -34- 200533651 in Figs. 4 and 9. Fresh feed benzene containing 400 to 800 wppm water in the line is purified in a conventional adsorbent container i 2 containing 1 μ of resin or clay adsorbent bed, removing the alkaline 〇NCs. The purified benzene in line 116 $ is optionally heated in a heat exchanger 丨 7 and transported to the thermal adsorbent container 160 in line 161. The thermal sorbent container 16o contains an acidic molecular sieve sorbent bed 162 for removing the NCs, and the nitriles contained in the line 161 from the purified benzene stream. The denitrification stage L in the bamboo line is combined with the combined sintering and trans-sintering effluent stream in the line 136 and is transported to the benzene column 140. The benzene column 140 produces the benzene contained in the line 142 丨The top stream of the benzene tower, and the bottom stream of the benzene tower containing ethylbenzene and PEBs in the official line 144. The top benzene stream in the line 142, can be provided with water concentration as high as 500 wppm, and the temperature疋 At least 120 ° C, and preferably greater than 125 °, and not more than 170 ° C. A portion of the overhead benzene stream in the official line 142J is diverted to the dealkylation reactor 150 via line 166 $. The DIB carried in the heavy column intermediate stream via line 168 is mixed with benzene at line 166 and provides a transalkylation feed stream in line 154. The DIB is in the transalkylation reactor 15 The transalkylation catalyst bed 156 is transalkylated with benzene to produce cumene. The transalkylation effluent in line 152 has a greater concentration of cumene and a lower concentration than those in line 1 54J. Benzene and DIB. The remainder of the benzene column overhead in line 102J is reacted with propylene on the alkylation catalyst bed in the alkylation reactor 120. As described in relation to Figure 4. The calcined effluent in line 1 26 J is mixed with the transalkylated effluent in line 52 to provide a combined effluent in line 136; ^ at line 144 The bottom stream of the benzene tower is transported to the cumene tower. 80. The isopropyl 98299.doc -35- 200533651 benzene tower 1 80 provides the cumene tower overhead stream containing the product cumene in line 182. Recovered. The cumene column bottom stream in line 184 contains heavier hydrocarbons than cumene and is transported to weight column 190. Weight column 190 produces an intermediate stream containing DIB in line 1 68 The lighter material in the top stream of the heavy column is removed in line 192, and the bottom stream of the heavy column is removed in line 194. It must be noted that in some illustrations, such as the receiver, reboiler, The equipment of the condenser and / or return line is detailed for some equipment, but not for others. However, the omission of this detail in the description and illustration does not indicate that the equipment is not tested. It will be known what kind of equipment is necessary. The present invention is further made clear by considering the following examples, which are intended to be pure Exemplary use of the present invention. Examples

Example I A test was performed to determine the effectiveness of acidic molecular sieves to adsorb acetonitrile from an aqueous benzene stream at low temperatures. The adsorbent was prepared by extruding about 80 weight percent zeolite and 20 weight percent alumina binder. After drying, the sorbent is crushed and the particles between 20 and 40 sieve are loaded into eight vessels in series fluid circulation. The benzene feed was saturated with 500 wppn ^ water and wppm acetonitrile supported, and passed through eight adsorbent vessels in series at room temperature and room pressure. The final loading was 0.125% by weight of adsorbed nitrogen relative to the adsorbent averaged over eight adsorbent beds. The adsorbent in the first five beds has its adsorption capacity, and acetonitrile passes through the bed in one day, and the adsorbent in the six to eight beds adsorbs its capacity in two days. 98299.doc -36- 200533651 Then, the adsorbent from the bed was washed with water at 50 ° C for one hour. Ninety-seven percent of the nitrogen is extracted from the sorbent. Therefore, at lower temperatures, water impairs the adsorption of acetonitrile and / or is better than acetonitrile being adsorbed.

Example II A series of tests were performed to compare the adsorption performance of clay, resin, and molecular sieve adsorbents for acetonitrile. The sorbent was loaded into eight vessels in series with fluid flow. The benzene feed was saturated with 500 wppm water, and each of the targets loaded with 1 wppm acetonitrile, NFM, and NMP flowed through eight sorbent vessels in series at room temperature and room sound. An experimental stupid feed had no water. Y zeolite is prepared by extruding about 80% by weight of Y-zeolite and 20% by weight of oxide binder. Table I compares the time it takes for organic nitrogen impurities to pass through the selected adsorbent bed.

Table I Adsorbent Clay (SC-626GS) Resin (A-15) Y Fossil Y Zeolite ~ Water Saturated Water Saturated Water Saturated 萆 ACN through the initial bed (days) immediately 0.9 immediately 0.1 ACN through the eighth bed (days) ) 1.6 0.8 _0.1 5.0 NMP passes the initial bed (days) 6.9 immediately 1_0.1 0.1 NMP passes the eighth bed (days) 30.6 > 15 > 7 > 8 NFM passes the initial bed (days) 6.9 Immediate 1 ~~ 〇7 \ ~~ 0.1 NFM passes through the eighth bed (day) i Nitrogen on the adsorbent > 30 〇15.0 — " L4 ~~ _6.7 ~ 09 ~~~ 7.0 ~~ 08 ~ Under the conditions, no bed can effectively adsorb acetonitrile for a long period of time. If a large bed is used, the zeolite can effectively absorb the appropriate amount from the dry feed. M Don't make μ | 13 1.4 Acetonitrile 'I is passed early because But the eighth bed is reasonably extended. Clay sorbents appear to be the best for NMρ and nfm. Resin appears to be only 98299.doc 200533651, which is a large bed of resin adsorbent, which properly adsorbs NMP and NFM, because passing through the initial bed is immediate, but extended in the eighth bed.

Formula III of Example III ^ # 系 歹] was performed to evaluate the removal of acetonitrile (ACN) from benzene by rubbing with about 80% by weight of γ. , Fu Shi and other weight% oxide Ming adhesive $ clothing preparation adsorbent contact. The sorbent has an ABD of 0.625 g / m³: For all tests, the sorbent was dried at 120 C for 2 hours after loading 25 g of sorbent into the container. The test was performed at 24 ° C and 150 ° C operating temperature, and the amount of water in the feed benzene was changed. The feed for the test was prepared with ACN tritium in a benzene stream to produce a target of about 20 WPPm lice. The starting benzene feed was dried before it was combined with ACN. In two of the tests, the benzene feed was combined with water to determine water versus nitrogen. The results of the four failed adsorbents analysis are summarized in Table II. ,

Table II Test No. Temperature (° C) Trace water content (wppm) Average failure adsorbent (wt%) 1 25 0 0.86 ~ 2 150 0 0.49 3 —150 50 1.07 ~ ^ 4 ~ 150 500 0.83 Table II " ugly It is believed that the addition of water to the feed improves the nitrogen capacity of the adsorbent at a temperature rise in the 150 ° C range. Tested at 50 wppm water at 150 ° C showed a nitrogen capacity of approximately 25% greater than that in anhydrous benzene feed at room temperature.

Example IV 98299.doc 200533651 The adsorbents from Test Nos. 2 and 3 in Shell Example I were subjected to thermogravimetric analysis (TGA) to determine the extent of coke accumulation on the adsorbents. The percentage of coke deposited on the sorbent and the temperature required to burn the coke from the sorbent are estimated and shown in the table claw.

Table III 2 8 3 < 1 Estimated combustion temperature (> 400 > 400 < 400 Based on TGA data, temperatures above 400 are required to burn coke from the adsorbent from test number 2. In addition, The amount of coke from the test sample No. 2, i 500c and the anhydrous adsorbent sample was about 8% by weight. Conversely, when the temperature increased by 400 ° C, the adsorbent from Test No. 3 did not show significant weight loss. It is estimated that the coke content of this adsorbent sample from the experimental test number 3 performed at 150 ° c & 50wppn ^ x is less than 1% by weight. Therefore, 'addition of water reduces coke formation on the adsorbent by more than 85%. When water is present during the adsorption of nitriles at elevated temperatures, the regeneration of the adsorbent will be less frequent. [Simplified illustration of the figure] Figure 1-3 describes the process for producing ethylbenzene according to the present invention. Figure 4-9 describes the present invention Production process of cumene. [Description of main component symbols] 8, 10, 10 ', 12', 14, 14a-f, pipelines 18, 32, 48, 52, 52, 54, 54, 98299.doc -39- 200533651 54 ', 56, 56', 58, 62, 66a-b, 68, 68, 74, 82, 84, 92 , 100, 101, 102, 102, 102 ,, 104, 104, 104a, M, 106, 106 ,,, 107, 110, 110, 110, 116, 116 ', 116ί , 126, 126J, 132, 132, 132 ', 132 ..., 132 卞, 133, 134, 135, 136, 136J, 142, 142J, 144, 152, 154, 154 ,, 154, 161, 161, 161 164, 164, 164 $, 166, 166, ', 166J, 168, 182, 184, 192, 194, 20 ~ 30, 120, 120, M, 120 | 20a-c, 30a-c 20d-f, 30d- f, 50a-50c, 122a-f, 122b, ', -fm 11, 117 40, 140 44, 112 46 50, 150, 150 ,, 150 | 58 alkylation reactor bed front space catalyst bed heat exchange Benzene tower conventional adsorbent container clay adsorbent bed transalkylation reactor transalkylation feed line condensation 98299.doc -40- 64 200533651 66 receiver 70, 160 thermal adsorbent container 72, 162, ', 162 ... , 162a, 162b Thermal adsorbent molecular sieve bed 80 Ethylbenzene column 90 PEB column 1 04a-e Feed inlet lines 106a-e, 106bMf-e 丨 "Distribution lines 124a-e, 157, 124a '" -e' , The space between the bed prop-off burner 130 156,156 ,,, 156t column alkylation catalyst bed 162 rpm acidic molecular sieve adsorbent bed 186 via line 188. Bypass control valve 190 weight cumene column 180 column 98299.doc 41

Claims (1)

200533651, A. Patent scope:-A method for separating organic nitridation a from a hydrocarbon stream, the method comprising: G, including water and organic nitridation, and the right to carry the weight> the dyeable hydrocarbon stream (68, 8 ), The organic nitrogen compound includes nitriles; the hafnium stream is in contact with the acidic molecular sieve in the nitrogen adsorption zone (72, 62) at least at present, and the recovered decontaminated hydrocarbon stream (0, 23) ), — ^ Includes nitriles at a lower concentration than the contaminated hydrocarbon ^. The method of claim item! Is characterized in that the contaminated smoke stream includes an aromatic compound. ι · 2. months. The method of item 1 or 2 is characterized in that the contact occurs at a temperature greater than 12 5 c. Shi Ming's method of claim 1, 2 or 3 is characterized in that no more than 1% by weight of dilute hydrocarbons is present in the contaminated hydrocarbon stream. The method of claim 1, 2, 3 or 4, characterized in that the contaminated hydrocarbon " L includes at least 20 wppm water. 6. The method of claim 1, 2, 3, 4 or 5, characterized in that the decontaminated hydrocarbon stream comprises a hydrocarbon alkylation matrix, and further comprising: feeding a first alkylation matrix comprising an alkylation matrix and impurities. The stream (12, 12 ')' passes through an impurity adsorption region (46, 114) containing a purified adsorbent, the adsorbent comprising clay or resin that selectively adsorbs the impurity, and the purified calcined matrix feed is recovered from the impurity adsorption region Stream (48, 48 ')' which contains an alkylating matrix and has an impurity concentration that is lower than the impurity concentration in the feed stream of the primary alkylating matrix; and 98299.doc 200533651 an alkylating agent, and at least a portion Parts of a purified alkylation matrix feed stream, and at least a portion of a decontamination hydrocarbon stream (10, 23) containing a hydrocarbon alkylation matrix, through an alkylation reaction zone (20, 30) containing an alkylation catalyst to The calcining agent burns the alkylation matrix to produce an alkylate, and a reaction effluent stream containing the alkylate is recovered from the alkylation reaction zone (18, 32). 7. The method of claim 6, wherein at least a portion of the purified calcined matrix feed stream is the contaminated hydrocarbon stream. 8. The method of claim 1, 2, 3, 4 or 5, further comprising: passing an alkylation matrix feed stream (48, 116) comprising a hydrocarbon alkylation matrix and an organic nitrogen compound to a separation zone (40, 130); recovering the contaminated hydrocarbon stream (68, 8) from the separation area, which includes a hydrocarbon burning matrix and an organic nitrogen compound; passing at least a part of the stream (丨 2, 12,) containing an alkylating matrix to Impurity adsorption area (46, 114) of an adsorbent that selectively adsorbs impurities (46, 114) 'The impurity contains a basic nitrogen compound; and the calcining agent and at least a part of the decontamination hydrocarbon stream (10, 23) containing the calcination matrix are passed to the calcination In the reaction zone (20, 30), the calcination matrix is oxidized with a calcining agent on the calcination catalyst to generate a calcined product, and a reaction effluent stream containing an alkylate is recovered from the calcined reaction region (18, 32 :). 9. The method according to claim 8, wherein the impurity adsorption region and the nitrogen adsorption region are spaced from the alkylation reaction region. 10. The method of claim 8, characterized in that the effluent stream (48, 11 6) from the impurity adsorption zone is the alkylated matrix feed stream. Π. — A burning system, including: 98299.doc 200533651 an impurity adsorption container (44, 112), which contains an inorganic or resin adsorbent (46, 114) to adsorb the impurity, and includes an alkylated matrix feed and feed D (12, 12 ') and purified alkylated matrix feed outlets (48, 48,); a nitrogen adsorption vessel (70, 160), containing a denitrogen adsorbent (2, 1 62), including selective adsorption Molecular sieves of nitrogen compounds, and including a purified matrix feed inlet (68, 161), which communicates downstream with the purified alkylated matrix feed inlet and denitrified alkylation matrix feed outlet (10, i 64); and an alkyl The alkylation reaction vessel (20, 30) contains an alkylation catalyst (20a_f, 30b), which is used to alkylate the alkylating agent and the alkylation substrate under the alkylation conditions, and includes ~ a burning reactor inlet (10, 18), communicating with the downstream of the denitrification and calcination matrix feed outlet and the alkylation reaction outlet (18, 32). 98299.doc