Method of obtaining alkylacetate

FIELD: chemistry.

SUBSTANCE: complex esters of carboxylic acids found application in paint-vanish and other branches of industry. Method of obtaining alkylacetate from acetic acid and alkene(s) C3-C5 or its(their) mixtures with saturated hydrocarbons is realised by contacting at higher temperature with solid strong-acid catalyst in one or several consecutive reaction zones with further separation of reaction mixture and isolation of concentrated alkylacetate by means of rectification, in which by regulation of reagent supply, temperature and cooling of flow(s) in each point of reaction zone(s) and on its (their) output, mole ratio acetic acid: alkene(s) not less than 1.2:1 and temperature not more than 120°C are supported, limitation of temperature is ensured by distributed supply of cold alkene-containing flow with temperature from minus 30 to plus 60°C into intermediate points of reaction zone(s) and/or between reaction zones possibly in combination with method(s) of cooling of reaction flows, selected from group, including: cooling reaction zone(s), cooling flows between reaction zones, cooling and recirculation of part of outgoing reaction mixture flow to input as minimum to first reaction zone.

EFFECT: efficient long-term catalyst functioning and obtaining pure product.

10 cl, 6 ex, 2 dwg

 

The invention relates to the field of production of esters of carboxylic acids (esters). More specifically the invention relates to the field of reception of allylacetate with high dissolving properties and which are used in paint and other industries.

Known methods for producing allylacetate, for example ethyl-, n-propyl and n-butyl by reacting acetic acid (CA) and the appropriate alcohol in the presence as catalyst of sulfuric acid or benzosulfimide, or para-toluenesulfonic acid [Reference oil. - L.: Chemistry, 1978, vol. 2, s-241].

The disadvantage of these methods is the high corrosivity of the used catalysts and their solutions, the release of a large amount of water, forming azeotrope with alcohols and received by esterase, and when receiving n-propyl and n-butyl - scarcity and high cost of alcohols With3-C4. In the process produce large quantities of environmentally harmful waste.

Known methods for producing esters of acetic acid by alkylation of the criminal code of the alkenes in the presence of boron fluoride and etilefrine boron fluoride [A.V.Topchiev. Selected works. - M.: Nauka, 1965, s-322]. The disadvantage of these methods is the high volatility and strong corrosivity kata is Satarov.

A known method of producing allylacetate, in particular second-butyl acetate (BWA), the alkylation of the criminal code of n-alkenes, in particular n-butenes, at elevated temperature and pressure in the presence of an acidic cation exchange resin with a significant molar ratio of n-alkenes : the criminal code, namely 1-3:1 [ed. mon. The USSR №560875, 05.06.77, bull. No. 21; J. go active. chemistry. - 1977, No. 3, s-644]. May be used in reaction zone temperature of from 70 to 110°C.

The examples use a significant molar excess of n-alkenes (n-butenes) in relation to the criminal code, namely 2:1. In this case, as shown by experimental verification, even at the lowest (of the specified interval) temperature largely occurring adverse reactions of di - and oligomerization of n-alkenes, which leads to rapid loss of catalyst activity - cation.

Produced in large quantities dimers and/or trimers of alkenes have azeotropy with the target allylacetate. Method of separation of alkyl acetate (BWA) from the above dimers and trimers in the ed. mon. No. 560875 not offered. In fact, in this author's testimony describes a method for mixtures containing ester, but is not given solutions to get Esther and concentrated to ensure the long life of the catalyst.

In Pat. US-5457228, 10.10.1995, method for obtaining lower allylacetate, according to which the wire is changed chemical interaction of the criminal code and propene or n-butene(s), perhaps in mixtures with alkanes, in a continuous reactor in the presence of sulfonic cation exchanger at a molar ratio of MC and n-alkene(s) in the diet from 1:1 to 2:1, keep the temperature at the inlet to the reactor during the synthesis of isopropylacetate from 70 to 120°With, in the synthesis of sec-butyl acetate from 80 to 120°leaving the reactor, the mixture is cooled to a temperature not lower than 70-80°and part of its recycle to the inlet of the reactor, and the amount of recycling is determined by the formula

- in the synthesis of isopropylacetate:

- during the synthesis of sec-butyl acetate:

where X is the mass ratio of the recirculated flow to the quantity of supply (raw materials),

And the molar ratio of the criminal code of the alkene(s) in the diet.

In Pat. EN-2176239, 21.06.2000, bull. Fig. No. 33, 27.11.2001, method for obtaining the BWA by chemical interaction of the criminal code and n-butenes in the presence of sulfonic cation exchanger in the cascade of reactors, and using the three reactors keep the temperature at the inlet to the first reactor 90-110°second 70-100°With the third 70-75°or in the presence of two reactors at the entrance to the first reactor 90-110°and at the entrance to the second 70-75°C.

This make recycling part of the cooled reaction mixture leaving each reactor, at the entrance to the reactor. Mass quantities of the recycle stream relative to the amount of raw materials is determined by the formula:

where X and concepts, similar to the above in U.S. Pat. US-5457228, and the molar ratio of butane to n-butenes in the feed butane-butenova mixture, n is the number of the reactor.

Very significant disadvantage of the methods in U.S. Pat. US-5457228 and U.S. Pat. EN-2176239 is that they provide for the conditions for the reaction zones, but only at the entrance to them, which do not guarantee the absence of excessive overshooting of the temperature in the reaction zones. Furthermore, they allowed to work without a molar excess of the criminal code in relation to alkenes: US-5457228 Pets molar ratio of the criminal code : alkenes MO=1:1, and in the claims RU-2176239 MO WK : alkenes generally not limited, i.e. it is allowed an excess of n-butenes. When a molar excess of n-butenes at the entrance to the reactor(s)at the specified mandatory recycling and no upper limit for X, in the reactor(s) will be an accumulation of n-butenes and their oligomerization. When permitted by the high temperatures at the inlet to the reaction zone (respectively 120 and 110° (C) and considerable heat when carrying out highly exothermic reactions + alkenes, the temperature inside the reactor can reach 150°and above, when a large formation of di - and oligomers of alkenes and deactivation of the catalyst inevitable.

Stated in US-5457228 selectivity of transformation in the alkyl acetate 89,5-94,3% is low, the if to consider, that a further separation of dimers and trimers of alkenes from alkyl acetate and the criminal code is very difficult, and their significant presence prevents the separation by distillation of the alkyl acetate from the criminal code.

Pat. US-5457228 and U.S. Pat. EN-2176239 require cooling of the total stream leaving the reaction mixture, and not only its recycled parts, which leads to unnecessary energy consumption. Pat. EN-2176239 requires an individual recirculation of the reaction mixture for each of the successive reactors, which unnecessarily complicates the process. In the formula Pat. EN-2176239 appear molar relationship of the criminal code : n-butenes and butane : n-butenes in raw materials (butane-butenova faction), and not on the input into the appropriate reactor. This is the reduced mass of the reactants in the conversion in the previous period(s), reactor(s). As a result, allowed by the patent conditions possible to obtain negative values of X. for Example, if A=1 and b=3 (25% n-butenes and 75% butane hydrocarbons) calculated for the third reactor, the value of X is minus to 0.127, which may not be in the determination of the ratio of two positive quantities.

Thus, these patents do not provide ways of ensuring necessary for industrial use long-term preservation of the activity of the catalyst and the production of clean alkyl acetate.

We have found the way to obtain the alkyl acetate(s) ISOC and alkene(s), providing effective long-term performance of the catalyst and obtain the pure product by maintaining a moderate temperature and a molar excess of the criminal code directly in the reaction zone and suppressing the formation of di - and oligomers alkenes.

We say:

The method of producing alkyl acetate from acetic acid and alkene(s)3-C5or his(their) mixtures of saturated hydrocarbons by contact at elevated temperature with a solid strong acid catalyst in one or more successive reaction zones, followed by separation of the reaction mixture and isolation of concentrated alkyl acetate using distillation, characterized in that by regulating the supply of reagents, temperature and cooling stream(s) support at every point of the reaction(s) area(s) and exit () the molar ratio of acetic acid : alkene(s) not less than 1.2:1 and a temperature of not more than 120°and setpoint provided by a distributed cold Alcantaras flow with temperatures ranging from minus 30 to plus 60°With, in the intermediate point of the reaction(s) area(s) and/or between the reaction zones, possibly in combination with the intake(s) cooling the reaction of threads, select(s) from the group comprising cooling the reaction(s) area(s), cooling p the currents between the reaction zones, cooling and recirculation of part of the exit stream of the reaction mixture at the entrance at least in the first reaction zone.

As options, promoting the effective use of the method according to claim 1, we also declare additional methods, characterized in that

- at each point of the reaction(s) area(s) out of it(them) keep the temperature no more than 100°C;

- temperature Alcantaras streams fed to an intermediate point of the reaction(s) area(s) and/or between the reaction zones, support up to 20°C;

as the solid strong acid catalyst used selfactivity catalyst;

from leaving the reaction(s) area(s) of the mixture or its precirculated of the original distilled unreacted hydrocarbons may consistently at high and moderate pressure, some of which may recycle to the reaction(s) area(s), then the alkyl acetate is separated from acetic acid by distillation and preferably subjected to drying heterotetramer rectification;

- as the source of the hydrocarbon stream using propene or a mixture of propane and the quality of the product receive isopropylacetate;

- upon receipt of isopropylacetate distilled off from the reaction mixture propane-propanolol fraction, subjecting it updat the additional rectification, in which output and recycle in the reaction(s) area(s) distillate with a high concentration of propene, and output VAT residue, containing predominantly propane;

- as the source of the hydrocarbon stream using n-butene(s) or his(their) a mixture of saturated hydrocarbons and the quality of the product receive second-butyl acetate;

- upon receipt of the second-butyl acetate, it is separated from acetic acid by distillation, carried out in the presence of water;

- as the source of the hydrocarbon stream using isopentane(s) and/or n-pentan(s), or their mixture with saturated hydrocarbons and the quality of the product(s) receive tert-pentalateral and/or second-pentalateral.

When using multiple reaction zones as such are defined as areas between which a cooling stream(s) and/or introduction of additional threads. When this reaction zone may be located in separate devices, and in the same vertical apparatus with radiative cooling and/or introduction of additional threads.

A significant positive effect is achieved by maintaining at all points in the reaction zone molar excess of acetic acid (CA) in relation to alkenes and moderate temperature, it is a discrete supply of part of cold Alcantaras flow in between the exact cross section of the reaction zone and/or between the reaction zones. This reduces the necessary circulation of the criminal code, as in the first reaction zone is supplied only part of alkenes, and the other(s) part(s) of alkenes comes(ut) stream(s), where most of the alkenes have been depleted in the formation of alkyl acetate. Served cold Alcantaras threads simultaneously perform the function of the refrigerant mixture. Specified allows you to virtually suppress the formation of di - and oligomers of alkenes, which is favourable for the operation of the catalyst due to the lack of blocking its active sites of the oligomers and to produce a concentrated alkyl acetate, with virtually no hard separable from it di - and trimers of alkenes.

The application of the invention illustrated in figures 1 and 2 and examples. These drawings and examples do not exclude the use of other technological options in compliance with the characteristics indicated in claim 1 of the claims.

According to figure 1 the synthesis of the ester is carried out in a vertical device P having three sequential reaction zones R-1, R-2 and R-3.

MC enters the system through line 1, and alkanolamide flow line 2. Thread 2 (possibly after connecting with recycled alkemadelaan flow) divided into three threads 2A, 2B and 2C, which respectively serve in the reaction zone R-1 (line 3), R-2 and R-3, and threads 2B and 2C are served without the agrimonia.

Thread 1 is combined with a recirculated stream of the criminal code, flows through the lines 9 and 6, and serves in zone R-1 line 2A (hereinafter referred to as line 3). Perhaps between the reaction zones provide cooling fluid through coolant HA.

From R-3 output line 4 to the reaction mixture, at least part of which is served by line 4A separation unit (UR). Perhaps part of the thread 4 is cooled and 4B (hereinafter, 5A, 6 and 3) served in the R-1. Part of the flow 4B possibly served in the R-2 and/or R-3 on lines 5B and 5B.

In UR reaction mixture (stream 4A) share at least a stream of unreacted hydrocarbons (line 7), the flow target of alkyl acetate (line 8) and the flow of the criminal code (line 9). Stream 7 is removed from the system through line 7a; possibly part of its line 6b recycle to the reaction apparatus P, mixing with the flow 2. Thread 9 recycle (lines 6 and 3) in R-1.

Figure 2 shows the synthesis of the ester in three separate sequential reaction zones R-1, R-2 and R-3 with interband cooling flows and the system of separation of the reaction mixture. Distribution and numbering streams feed into the reaction zone, and a stream output similar to the one shown in figure 1.

The flow of the reaction mixture 4A enters the apparatus K-1 for distillation of unreacted hydrocarbons. The top on line 7 display distilled hydrocarbons, which are further removed from the system through line 7a and/sludge is partially recycled to the reaction site on line 7b, and/or (when getting isopropylacetate) served in the distillation column K-4. Top-To-4 line 9 output propene-propane flow to the high concentration of propene (its recycle to the reaction site), and the bottom line 10 output propane stream.

Bottom-To-1 line 8 output stream containing primarily a mixture of alkyl acetate and the criminal code, which is sent to distillation column K-2.

From the bottom of the K-2 display of the criminal code (threads 12 and/or 12A), which recycle to the reaction site. Top K-2 output alkyl acetate on line 13 and further 13A. You can stream alkyl acetate on line 13B is fed to the column azeotropic dehydration K-3. Bottom-To-3 line 14 deduce dry alkyl acetate, and the top (from the pit) output stream 15 containing predominantly water.

In the separation of the second-butyl acetate (BWA) from AC rectification in K-2 is carried out in the presence of water, which prepare the chin from the BWA in the sump and About on line 12 return To 2.

Examples

In the examples, the concentration indicated in wt.%. Used abbreviations: MC - acetic acid, propane - propene-propane fraction, BBF - butane-n-butenova fraction, IPA - isopropylacetate, BWA - sec-butyl acetate, dimers (trimers), respectively dimers (trimers) alkene(s), SOY - static exchange capacity of the catalyst in mEq/g·cat, MO molar ratio of the criminal code : reacting(e) alkene(s).

p> Comparative example (as per prototype).

Synthesis of BWA conducted from the criminal code and BBF (n-butenes and butane in a 1:1 ratio) in accordance with U.S. Pat. EN-2176239 in the system with three consecutive reactors sulfonic cation exchanger (SOY=4). MO WK : n-butenes was 1:1, the temperature at the entrance of the reactor, respectively 110°, 100°and 75°C. the Calculated coefficient of recirculation (n=1) X=3,5. Conversion of n-butenes was 82%, the selectivity of their transformation in the BWA 90-92% (rest - dimers and oligomers).

After 150 hours marked by the deposition of polymers on the surface of the catalyst and reduce its activity (SOYBEAN) by 10-15%.

The remaining examples illustrate our invention.

Example 1.

Obtaining IPA conduct of the criminal code and propane, containing 75% of propene, in accordance with figure 1.

In the reaction zone loaded fine-grained (0.3 to 1.3 mm) sulfonation on the basis of a copolymer of styrene and divinylbenzene with SOY-value of 5.0.

The criminal code in the number 96,0 kg/h fed into the process through line 1, then line 3 to P-1. Cold PPF (minus 20° (C) in an amount of 100 kg/h fed into the process through line 2. Thread 2 distribute flows 2A, 2B, 2C in the ratio of 45:35:20. Stream 1 attach the recirculated flow 9 of the criminal code (19,2 kg/h).

On the inputs and outputs of the reaction zone (RZ) threads have the following temperature and MO WK : propene:

Temperature, °MO
Zone R-1input702,4
output8614,9
Zone R-2input701,7
output854,6
Zone R-3input721,3
output811,9

The total conversion of propene in the device R is ˜90%. From P in line 4 display 216,4 kg/h stream containing 11.6% propane, 3,3% of propene, 8,9% of the criminal code, 76,0% IPA, 0.3% of di - and trimers.

Stream 4 is served in the node splitting UR and from the output lines 7a and 32.3 kg/h propane-propanolol mixture (22.4% of propene), 8 output 164,3 kg/h of flow of the IPA (the concentration of 99.7%, the rest of di - and trimers) and on the output line 9 of 19.8 kg/h of the criminal code (return to R-1).

Over 1400 hours of work is not found to reduce the activity of the catalyst and polymer deposits in the equipment.

Example 2.

Obtaining IPA carried out according to figure 2 in the main while maintaining the temperature, proportions of threads and MO mentioned in example 1, with the same catalyst.

Unlike example 1 PPF (threads 2B and 2C) served with a temperature of 20°and in the scheme and the column is K-4. The conversion of propene in total R-1, R-2, R-3 for pass ˜75%, the total conversion of propene in the process (including recycling) of 99%. Distilled from the reaction mixture stream 7 served in the distillation column K-4, where the top place and return to the stream PPF (stream 2) propene-propane mixture with a concentration of 65% of propene, and bottom derive mainly propane (˜25,0 kg/h).

After separation from the criminal code in K-2 on line 13 deduce 180,2 kg/h IPA concentration 99,6% (the rest of di-and trimers of propene and water admixture).

Alternatively IPA is subjected to azeotropic dehydration in K-3 and below its output dry IPA.

After 1000 hours no decrease in catalyst activity and polymer deposits.

Example 3.

Getting the BWA carried out according to figure 1 of the criminal code and BBF, containing ˜50% n-butenes and ˜50% butane. Use selfactivity the catalyst having SOY=4,1.

The criminal code in the amount of 5.1 kg/h fed into the process through line 1 (after mixing with recycle of the criminal code and part of the PPF line 3). Cold (10° (C) BBF in the amount of 100 kg/h fed into the process through line 2. Thread 2 distribute flows 2A, 2B and 2C in the ratio of 50:35:15.

On the inputs and outputs of the reaction zone flows have the following temperature and MO MC/n-butenes:

Temperature, °MO
Zone R-1 input802,30
output938,10
Zone R-2input791,65
output923,80
Zone R-3input771,55
output863,10

The total conversion of n-butenes in R is 92-93%. From P in line 4 display and served in UR 161,4 kg/h stream containing 31.0% butane, and 2.0% n-butenes, 6.7% of the criminal code, 60.0% of the BWA, 0.3% dimers.

From UR of the output lines 7 and 7a 53,2 kg/h butane-butenova mixture (94,0% butane and 6.0% n-butenes), 8 output to 96.9 kg/h of BWA with the concentration of 99.5% (the rest of di-and trimers) and 9 display 11.3 kg/h of the criminal code (˜4% BWA), which return in R-1.

After 1440 hours not detected decrease in catalyst activity and polymer deposits.

Example 4.

Getting the BWA carried out according to figure 2 in the main while maintaining the temperature, the proportions of threads that mentioned in example 3, with the same catalyst.

Unlike example 3, half of the thread 4 is cooled to 80-85°and a recycle line 46 (hereinafter 5A, 6 and 3) in R-1. From the rest of the thread 4 in the K-1 distilled butane-butenova mixture (˜3% butenes), half of which (51,5 kg/h) conclusion the Yat line 7a, and the other half recycle line 7b, then 11, mixing with the flow 2.

Conversion of n-butenes in the process (including recycling) is 96%.

Remaining in Cuba To-1 mixture (stream 8) is served in a distillation column K-2, where BWA is separated from the criminal code in the presence of water. On line 13 deduce 100,9 kg/h of BWA with the concentration of 99.5% (the rest of the dimers). On line 12 output of 10.7 kg/HR bldg 3% of BWA, which recycle in R-1.

Alternatively, the BWA is subjected to azeotropic dehydration in K-3 and below on line 14 deduce dry BWA.

After 1000 hours no reduction activity of the catalyst and formation of polymer deposits.

Example 5.

Obtain tert-pistillata (TPA) is conducted according to figure 1 of the criminal code and pentane-pentenol fraction containing a total of 30% of pentanol (2-methyl-1-butene and 2-methyl-2-butene in a ratio of 1:1,7). Use selfactivity the catalyst having SOY=4,3. The criminal code in the number 24,2 kg/h fed into the process through line 1 (after mixing with recirculated criminal code and part pentane-pentenol faction - line 3).

Cold (25° (C) pentane-pontenova fraction fed into the process through line 2 in the amount of 100 kg/h Thread 2 distribute the threads 2, 2B and 2C in the ratio of 50:35:15.

On the inputs and outputs of the reaction zone flows have the following temperature and MO UC/tert-pentene:

Area Entrance, °Exit °MO (input)MO (output)
P-145652,87,5
R-245642,14,4
R-343522,07,8

Conversion of tert-pentanol in the process of 90-92%.

The site of UR, after distillation, unreacted hydrocarbon, C5The company is distilled from TPA in the composition of the distillate by distillation in the presence of relatively high-boiling (100-125° (C) saturated hydrocarbons and return to P-1.

From UR of the output of 91.8 kg/h of stream 7 (hydrocarbon, C5content of 2.5% tert-pentanol), 53,8 kg/h of stream 8 (97,4% TPA, 0.7% of dimers, 1.9% of high-boiling saturated hydrocarbons) and 17 kg/h of stream 9 (70,7% of the criminal code, 5.8% of TPA, with 23.5% of high-boiling saturated hydrocarbons). Thread 9 recycle in R-1.

Over 900 hours of work is not found to reduce the activity of the catalyst and formation of polymer deposits.

Example 6.

Obtaining IPA carried out according to figure 1 of the criminal code and concentrated propene (99.9% of propene, the rest is a mixture of propane). Use molded selfactivity catalyst KU-FPP (granules with a diameter of 4-5 mm, 5-7 mm in length, SOY-3,5).

The criminal code in the amount of 90 kg/h fed into the process through line 1, hol the command propene (minus 20° (C) in the amount of 63 kg/h fed into the process through line 2. Thread 2 distribute flows 2A, 2B and 2C in the ratio of 40:35:25. Stream 1 attach the recirculated flow 9 of the criminal code, the thread 2 is attached 7b recirculated flow of propene.

In the reactor support the conversion of propene 75%, after distillation of the product in UR in the reaction zone (initially in line 2) return of 15.75 kg/h of propene. From UR input in P-1 (line 9, 6) return 135 kg/h of the criminal code.

On the inputs and outputs of the reaction zones keep the temperature (° (C): area P-1 - input 60, exit 75; area P-2 - input 63, the output 78; zone R-3 - input 63, exit 77. At all points in the reaction zone MO WK : propene significantly higher than 1.2:1.

On line 4 of P-3 output stream 307 kg/h, which is dominated by the criminal code, IPS and propene. From a node split UR on line 8 output 153 kg/h of a stream containing predominantly IPA (99,6%), the rest of di - and trimers of propene.

After 1000 hours of operation is not detected polymer deposits in the equipment. SOY sulfonates of the catalyst is decreased by a small amount and was 3.4.

1. The method of producing alkyl acetate from acetic acid and alkene(s)3-C5or his(their) mixtures of saturated hydrocarbons by contact at elevated temperature with a solid strong acid catalyst in one or more successive reaction zones and subsequent times is the bookmark of the reaction mixture and isolation of concentrated alkyl acetate using rectification, characterized in that by regulating the supply of reagents, temperature and cooling stream(s) support at every point of the reaction(s) area(s) and exit () the molar ratio of acetic acid : alkene(s) not less than 1.2:1 and a temperature of not more than 120°C, and the temperature limit provided by distributed cold Alcantaras flow with temperatures ranging from minus 30 to plus 60°in the intermediate point of the reaction(s) area(s) and/or between the reaction areas possibly in combination with the intake(s) cooling the reaction of threads, select(s) from the group comprising cooling the reaction(s) area(s), cooling flows between the reaction zones, cooling and recirculation of a part of the exit stream of the reaction mixture at the entrance at least in the first reaction zone.

2. The method according to claim 1, characterized in that in each point of the reaction(s) area(s) out of it(them) keep the temperature no more than 100°C.

3. The method according to claim 1, characterized in that the temperature Alcantaras streams fed to an intermediate point of the reaction(s) area(s) and/or between the reaction zones, support up to 20°C.

4. The method according to claim 1, characterized in that, as specified solid strong acid catalyst used selfactivity catalyst.

5. The method according to P1, characterized in that of the output from the reaction(s) area(s) of the mixture or its precirculated of the original distilled unreacted hydrocarbons may consistently at high and moderate pressure, some of which may recycle to the reaction(s) area(s), then the alkyl acetate is separated from acetic acid by distillation and preferably subjected to drying heterotetramer rectification.

6. The method according to claim 1, characterized in that as the source of the hydrocarbon stream using propene or a mixture of propane and the quality of the product receive isopropylacetate.

7. The method according to claim 1, characterized in that when receiving isopropylacetate distilled off from the reaction mixture propane-propanolol fraction, subjecting it to additional rectification, in which output and recycle in the reaction(s) area(s) distillate with a high concentration of propene and output VAT residue, containing predominantly propane.

8. The method according to claim 1, characterized in that as the source of the hydrocarbon stream using n-butene(s) or his(their) a mixture of saturated hydrocarbons and the quality of the product receive second-butyl acetate.

9. The method according to claim 1, characterized in that when receiving second-butyl acetate, it is separated from acetic acid by distillation, carried out in the presence of water.

10. The method according to claim 1, characterized in that as the source of the hydrocarbon stream using isopentane(s), and/or n-pentan(s), or their mixture with saturated hydrocarbons and the quality of the product(s) receive tert-pentalateral and/or second-pentalateral.



 

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30 cl, 1 dwg, 5 tbl, 14 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to improved C2-C4-alkane oxidation process to produce corresponding alkene and carboxylic acid, which process comprises bringing indicated alkane in oxidation reaction zone into contact with molecular oxygen-containing gas and corresponding alkene and optionally with water in presence of at least one catalyst efficient for oxidation of alkane into corresponding alkene and carboxylic acid. Resulting product contains alkene, carboxylic acid, and water, wherein alkene-to-carboxylic acid molar ratio in oxidation reaction zone is controlled or maintained at desired level by way of controlling alkene and optional water concentrations in oxidation reaction zone and also, optionally, controlling one or several from following parameters: pressure, temperature, and residence time in oxidation reaction zone. Invention also relates to integrated process of producing alkyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone in contact with each other in presence of at least one catalyst effective in production of alkyl carboxylate to produce the same. Invention further relates to production of alkenyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone plus molecular oxygen-containing gas into contact with each other in presence of at least one catalyst effective in production of alkenyl carboxylate to produce the same.

EFFECT: enhanced process efficiency.

55 cl, 1 dwg, 7 tbl, 22 ex

FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.

SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

44 cl, 3 ex, 6 dwg

Cleaning method // 2237652
The invention relates to an improved method of purification of the reaction products of the process of direct connection, comprising the reaction of ethylene with acetic acid in the presence of an acid catalyst to obtain ethyl acetate, and cleaning products, recycling, and this cleaning method includes the following stages: (I) feeding the reaction product in column (A) to remove the acid from the base which divert acetic acid, and with its top pick at least a fraction comprising boiling components containing, inter alia, hydrocarbons, ethyl acetate, ethanol, diethyl ether and water, and is directed to the apparatus (A1) for decanting in order to share these top shoulder straps on the phase rich in ethyl acetate, and water (rich in water) phase, (II) a separate return at least part of the rich ethyl acetate phase and almost all of the aqueous phase from the apparatus (A1) for decanting as phlegmy in the upper part of the column (A) or near its top, (III) the filing of the rest of the rich ethyl acetate phase from the apparatus (A1) for decanting in the upper part of the Westfalia refinery unit column (s) or near its top, (IV) the removal from the column (C): and nedogona, including significantly refined ethyl acetate, which is directed to the treatment of the colon is his, acetaldehyde and diethyl ether, which is sent to the column to remove aldehyde, and (C) lateral fraction comprising mainly ethyl acetate, ethanol and some water, which is directed to a point below the point of entry is rich in ethyl acetate phase is removed from the column (A), (V) challenging reset, including acetaldehyde, from the top or near the top of the column for removal of aldehyde and return diethyl ether, isolated from the base of the column to remove aldehyde, etherification reactor and (VI) purification of refined ethyl acetate in column (E)

The invention relates to a method for producing acetic acid and/or methyl acetate in the liquid phase, in the presence of carbon monoxide and the catalytic system, and to a method of increasing the stability and lifetime of the catalyst utilized

Synthesis of esters // 2227138
The invention relates to an improved method for producing a lower aliphatic esters, including the interaction of lower olefin with a saturated lower aliphatic monocarboxylic acid, preferably in the presence of water in the vapor phase in the presence of heteropolyanions catalyst, characterized in that the reaction is carried out sequentially placed in several reactors or in one long reactor with several successive layers heteropolyanions catalyst and b) initial reagents practically cleared of metallic impurities or compounds of metals so that before coming in contact with heteropolyanions catalyst metals and/or metal compounds is not more than 0.1 ppm

The invention relates to the production of acetic acid and/or methyl acetate

The invention relates to an improved process for the preparation of butyl acetate by esterification of acetic acid n-butyl alcohol in the presence of an acidic heterogeneous catalyst, separating the resulting reaction water in the form of an azeotrope with azeotropes agent and the selection of the target product, and acetic acid and n-butyl alcohol is fed to the etherification in a molar ratio of 1.00: 1,05, and the process is conducted in two sequential reactors, the first of which is a column type reactor filled with an acidic heterogeneous catalyst, and the second is a reactive distillation reactor, the upper and lower part of which is filled by the nozzle, and the middle part is filled molded cation exchange resin, and in the upper part of the second distillation reactor serves benzene as azeotroping agent

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for oxidation of (C2-C4)-alkane and preparing the corresponding alkene and carboxylic acid. Method involves addition of this alkane to contact with molecular oxygen-containing gas in oxidative reaction zone and optionally at least one corresponding alkene and water in the presence of at least two catalysts with different selectivity. Each catalyst is effective in oxidation of alkane to corresponding alkene and carboxylic acid resulting to formation of product comprising alkene, carboxylic acid and water wherein the molar ratio between alkene and carboxylic acid synthesized in the reaction zone is regulated or maintained at the required level by regulation the relative amounts of at least two catalyst in the oxidative reaction zone. Also, invention relates to the combined method for preparing alkyl carboxylate comprising abovementioned stage in preparing alkene and carboxylic acid in the first reaction zone. Then method involves the stage for addition of at least part of each alkene and carboxylic acid prepared in the first reaction zone to the inter-contacting in the second reaction zone the presence of at least one catalyst that is effective in preparing alkyl carboxylate to yield this alkyl carboxylate. Also, invention relates to a method for preparing alkenyl carboxylate comprising the abovementioned stage for preparing alkene and carboxylic acid in the first reaction zone and stage for inter-contacting in the second reaction zone of at least part of each alkene and carboxylic acid synthesized in the first reaction zone and molecular oxygen-containing gas in the presence of at least one catalyst that is effective in preparing alkenyl carboxylate and resulting to preparing this alkenyl carboxylate.

EFFECT: improved method for oxidation.

30 cl, 1 dwg, 5 tbl, 14 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to improved C2-C4-alkane oxidation process to produce corresponding alkene and carboxylic acid, which process comprises bringing indicated alkane in oxidation reaction zone into contact with molecular oxygen-containing gas and corresponding alkene and optionally with water in presence of at least one catalyst efficient for oxidation of alkane into corresponding alkene and carboxylic acid. Resulting product contains alkene, carboxylic acid, and water, wherein alkene-to-carboxylic acid molar ratio in oxidation reaction zone is controlled or maintained at desired level by way of controlling alkene and optional water concentrations in oxidation reaction zone and also, optionally, controlling one or several from following parameters: pressure, temperature, and residence time in oxidation reaction zone. Invention also relates to integrated process of producing alkyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone in contact with each other in presence of at least one catalyst effective in production of alkyl carboxylate to produce the same. Invention further relates to production of alkenyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone plus molecular oxygen-containing gas into contact with each other in presence of at least one catalyst effective in production of alkenyl carboxylate to produce the same.

EFFECT: enhanced process efficiency.

55 cl, 1 dwg, 7 tbl, 22 ex

Cleaning method // 2237652
The invention relates to an improved method of purification of the reaction products of the process of direct connection, comprising the reaction of ethylene with acetic acid in the presence of an acid catalyst to obtain ethyl acetate, and cleaning products, recycling, and this cleaning method includes the following stages: (I) feeding the reaction product in column (A) to remove the acid from the base which divert acetic acid, and with its top pick at least a fraction comprising boiling components containing, inter alia, hydrocarbons, ethyl acetate, ethanol, diethyl ether and water, and is directed to the apparatus (A1) for decanting in order to share these top shoulder straps on the phase rich in ethyl acetate, and water (rich in water) phase, (II) a separate return at least part of the rich ethyl acetate phase and almost all of the aqueous phase from the apparatus (A1) for decanting as phlegmy in the upper part of the column (A) or near its top, (III) the filing of the rest of the rich ethyl acetate phase from the apparatus (A1) for decanting in the upper part of the Westfalia refinery unit column (s) or near its top, (IV) the removal from the column (C): and nedogona, including significantly refined ethyl acetate, which is directed to the treatment of the colon is his, acetaldehyde and diethyl ether, which is sent to the column to remove aldehyde, and (C) lateral fraction comprising mainly ethyl acetate, ethanol and some water, which is directed to a point below the point of entry is rich in ethyl acetate phase is removed from the column (A), (V) challenging reset, including acetaldehyde, from the top or near the top of the column for removal of aldehyde and return diethyl ether, isolated from the base of the column to remove aldehyde, etherification reactor and (VI) purification of refined ethyl acetate in column (E)

Synthesis of esters // 2227138
The invention relates to an improved method for producing a lower aliphatic esters, including the interaction of lower olefin with a saturated lower aliphatic monocarboxylic acid, preferably in the presence of water in the vapor phase in the presence of heteropolyanions catalyst, characterized in that the reaction is carried out sequentially placed in several reactors or in one long reactor with several successive layers heteropolyanions catalyst and b) initial reagents practically cleared of metallic impurities or compounds of metals so that before coming in contact with heteropolyanions catalyst metals and/or metal compounds is not more than 0.1 ppm

The invention relates to a method for the synthesis of esters from olefins and lower carboxylic acids

The invention relates to an improved process for the preparation of secondary butyl alcohol, which is an intermediate for the production of methyl ethyl ketone

The invention relates to an improved method for producing sec-butyl acetate is used as solvent for paints and varnishes and as raw material for the production of sec-butyl alcohol

The invention relates to chemical technology, in particular to a method for producing sec-butyl acetate (BWA), used as a solvent for paints and varnishes and for the production of sec-butyl alcohol
The invention relates to an improved method for producing a complex terpene esters in the application of the solid catalyst

FIELD: petrochemical processes.

SUBSTANCE: invention relates to improved C2-C4-alkane oxidation process to produce corresponding alkene and carboxylic acid, which process comprises bringing indicated alkane in oxidation reaction zone into contact with molecular oxygen-containing gas and corresponding alkene and optionally with water in presence of at least one catalyst efficient for oxidation of alkane into corresponding alkene and carboxylic acid. Resulting product contains alkene, carboxylic acid, and water, wherein alkene-to-carboxylic acid molar ratio in oxidation reaction zone is controlled or maintained at desired level by way of controlling alkene and optional water concentrations in oxidation reaction zone and also, optionally, controlling one or several from following parameters: pressure, temperature, and residence time in oxidation reaction zone. Invention also relates to integrated process of producing alkyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone in contact with each other in presence of at least one catalyst effective in production of alkyl carboxylate to produce the same. Invention further relates to production of alkenyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone plus molecular oxygen-containing gas into contact with each other in presence of at least one catalyst effective in production of alkenyl carboxylate to produce the same.

EFFECT: enhanced process efficiency.

55 cl, 1 dwg, 7 tbl, 22 ex

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