The method of obtaining alkanols and glycols
(57) Abstract:Lower monobasic and dibasic alcohols receive, through the following stages: a) the interaction of the source with the halide of the divalent metal (where the metal is in the higher of two possible valence States) to obtain a reaction product corresponding to the halides of monovalent metal (where the metal is in the lower of the two possible valence States) and halogen acids; b) interaction of the reaction product from stage (a) and halogen acids with magnesium oxide to obtain the corresponding lower monobasic or dibasic of alkanol, where the original product to receive the lower monobasic alcohol is a lower alkane, from which to obtain the corresponding lower alkanol, and the source product to receive the lower dibasic alcohol is either the lowest alcol or lower alkene, of which receive the respective lower glycol. To carry out the necessary reactions proposed two continuous system with fluid layers. The proposed method allows to simplify the process of synthesis and can be used in the field of organic chemistry. 3 S. and 12 C.p. f the th alkylchloride. The interaction of the obtained alkylchloride with magnesium oxide and steam leads to receipt of alkanol. Similarly, lower alkenes or lower alkanols converted into the corresponding glycols.Previously methane were chlorinated with gaseous chlorine or were subjected to oxychloination under the action of oxygen and hydrochloric acid to obtain methyl chloride along with other chlorides, such as dichloromethane, trichloromethane and carbon tetrachloride. In this way of haloiding methane is formed hydrochloric acid. This hydrochloric acid should be removed, digidrirovanne by azeotropic distillation and recycled.Then distilled hydrolyzing chlorine-methanes in the vapor phase to methanol, formaldehyde, formic acid, carbon dioxide and hydrochloric acid. The resulting compositions depend on the selectivity of chlorination to methyl chloride and other chlorides. When this material are corrosion and difficulties associated with the handling of chlorine and hydrochloric acid.The purpose of the invention is to overcome or exclusion of pre-existing problems and creating simple method of conversion of alkane in soota.In accordance with this method, methane (preferred alkane) is subjected to interaction with the metal chloride (chloride ferrous metal, where the metal is in the higher of two possible valence States with the receipt of methyl chloride, the corresponding metal chloride (chloride monovalent metal), in which the metal is in the lower of the two possible valence States, and hydrochloric acid. The obtained methyl chloride and hydrochloric acid is subjected to interaction with magnesium oxide to methyl alcohol and hydrate of magnesium chloride. The obtained chloride monovalent metal is subjected to interaction with hydrochloric acid and oxygen to produce a chloride of the divalent metal, and the hydrate of magnesium chloride is converted into magnesium oxide and hydrochloric acid. Similarly, lower alkenes is converted into the corresponding glycols.In Fig. 1 is a flow diagram of one implementation of the claimed method; Fig. 2 - flow chart of another and a simplified implementation of the claimed method.Methane is subjected to interaction with the chloride of the metal, which is able to gloriavale. In kacher, chloride divalent copper interacts with methane to form methyl chloride, chloride of monovalent copper and hydrochloric acid according to reaction (I)
2CuCl2+ CH42CuCl + CH3Cl + HCl. (I)
Then the obtained methyl chloride and hydrochloric acid is subjected to interaction with steam and a catalyst containing magnesium oxide, in accordance with reaction scheme (II) 2 H2O + CH3Cl + HCl + MgO CH3OH + MgCl2+ H2O. (II)
The air and oxygen is passed in countercurrent through the magnesium chloride in order to allocate hydrochloric acid according to reaction scheme (III)
MgCl2xH2O MgO + 2HCl, (III)
and then through the monovalent chloride copper with obtaining newly chloride divalent copper in accordance with reaction scheme (IV)
2 HCl + 1/2 O2+ 2CuCl 2CuCl2+ H2. (IV)
Reaction (I) is conveniently carried out at a temperature of from 300 to 360oC, for which there is no formation of chlorine through the decomposition of chloride of divalent copper. This decomposition takes place at 993oC with the formation of chlorine. By maintaining a low temperature, the possibility of further chlorination of methyl chloride to the highest chlorides are reduced to a minimum.Reaction (III) is conveniently carried out at a temperature of approximately 200oC, and the reaction of (IV) convenient to carry out approximately in the temperature range from 300 to 380oC.The preferred method is a continuous process, which uses a fluidized bed reactor. However, the use of rectors of the fluidized bed is optional and can be used reactors with batch loading. Instead of metal chloride, for example, copper chloride, the reaction (I) can be used in the mixture. The preferred mixture is a mixture of ferrous chloride copper chloride monovalent copper, and magnesium oxide. This particular mixture is preferably used for the chlorination of methane, because the dilution of chloride of copper, magnesium oxide formed less chlorinated methylchloride. In addition, when the re-oxidation in the presence of hydrochloric acid formed magnesium chloride interacts with any of the formed copper oxide with getting chloride of copper. Magnesium oxide is also used to increase porosity
MgCl2+ CuO MgO + CuCl2. (V)
Excess chloride monovalent copper adsorbs any generated chlorine
CuCl + 1/2 Cl2CuCl2. (VI)
Instead of Olite for hydrolysis of methyl chloride to methanol and hydrochloric acid; if 200oC hydrochloric acid adsorbed further magnesium oxide. At temperatures above 115oC is formed MgCl24H2O fully adsorbing all of hydrochloric acid, which can be re-allocated by heating it to 200oC when passing through the air.The mechanism and kinetics of thermal decomposition of hydrates of magnesium chloride described (Kirk-Othmer Encyclopedia of Chemical Technology, vol. 14-623, 3d Edition). Reactions that are reversible, proceed in the following stages:
95-115oC MgCl26H2O MgCl24H2O + 2H2O;
135-180oC MgCl24H2O Mg(OH)Cl + HCl + 3H2O;
186-230oC MgCl2H2O Mg(OH)Cl +HCl;
230oC Mg(OH)Cl +HCl.The advantages are a consequence of these properties of the hydrates of magnesium chloride to adsorb and re-allocate hydrochloric acid.Extremely high conversion of methyl chloride in methyl alcohol (almost 100%) at the expense of the magnesium form of the zeolite (MgZ2) can be explained by the following reactions:
MgZ2+ 2CH3Cl MgCl2+ 2CH3Z,
CH3Z + H2O HZ + CH3OH
MgCl2+H2O Mg(OH)2+ 2HCl,
Mg(OH)2+2HZ MgZ2+2H2the use of a typical continuous process using fluidized bed reactor, methane is served in fluidization 2 to line 1, where it interacts with ferrous chloride copper contained in the fluid reagent 5, consisting of a mixture of magnesium oxide, ferrous chloride and copper chloride monovalent copper. (Alternatively, you can use the ferrous bromide and copper bromide monovalent copper). The reacted gas, consisting mainly of hydrochloric acid, methyl chloride and excess methane, is fed via line 3 to the cyclone 4, from which dust particles are returned to the reactor 2. The gas leaving the cyclone 4 and the pipe 6, into the reactor 7, which contains the catalyst (magnesium zeolite) 41, together with the steam, which flows through the pipe 33. The reacted gases containing methyl alcohol, hydrochloric acid and an excess of methane, leave the reactor 7 through the pipe 8, which directs them in fluidization 9 containing magnesium oxide 42, adsorbing all of hydrochloric acid.Gases leaving fluidization 9 through the pipe 10 into the cyclone 11, from which dust particles are returned in fluidization 9, contain methyl alcohol and excess methane. These gases are served by pipeline 12 to the condenser 13, where methyl Speer the capacitor 13 through the pipe 14 to the exhaust valve 17 and pipe 15 into the compressor 16, which returns excess methane to pipeline 1.The spent reagent 5 of fluidization 2 flows through the pipe 18 into fluidization 19, where it meets a stream of gas containing air and hydrochloric acid; chloride monovalent copper in it regenerated again in the form of chloride of divalent copper.The regenerated reagent 20 is supplied through pipe 21, where he meets transporting gas air 22, which raises his pipe 23 into the cyclone 24, where transport the gas (air) is manufactured by pipe 25 to the atmosphere, and the compound 5 is fed through a cyclone 24 in fluidization 2.Gases from fluidization 19 containing the possible traces of hydrochloric acid, are fed via pipe 26 into the cyclone 62, from which dust particles are returned in fluidization 19, and the liberated gases by pipeline 27 - fluidization 28, which contains magnesium oxide 32, he and adsorbs all traces of hydrochloric acid. The purified gas is discharged into the atmosphere through the pipe 29 and the cyclone 30, which returns the pulverized particles in fluidization 28, and produced a clean gas without impurities through the conduit 31.Exhaust magnesium oxide 32 leaves fluidization exhaust magnesium oxide 37. The regenerated magnesium oxide send pipeline 56, here transporting gas 40 raises his pipe 39 into the cyclone 57. Transport gas release pipe 58 to the atmosphere, and the regenerated magnesium oxide comes in fluidization 28. Gases leaving the reactor fluidized bed 34, containing air and hydrochloric acid, are sent to the pipe 35 into the cyclone 36, where dust particles are returned in fluidization 34, and the gases are served by pipe 60 into the pipe 59.Exhaust magnesium oxide 42 leaves the reactor with a fluidized bed 9 through the pipe 43, which directs it into fluidization 47, where it meets a stream of air introduced through the pipeline 50, which regenerates the spent magnesium oxide 48. The regenerated magnesium oxide is fed via a pipe 51, here he is met by the transport gas (air) 52, which raises it to the cyclone 54 through the pipe 53. The transport gas is discharged through the pipe 55, and the cyclone 54 sends the regenerated magnesium oxide in fluidization 9.Gases leaving fluidization 47 containing hydrochloric acid and air, are sent to the pipe 44 into the cyclone 45, where dust particles who is od 59 and together with the gases from the pipe 60 are received in fluidization 19.The air enters in fluidization 34 by pipeline 49; the air enters in fluidization 47 through the pipeline 50.Temperatures indicated in Fig. 1 are illustrative. Reagent 5 receives, for example, mixing the ferrous chloride copper chloride monovalent copper, and magnesium oxide, in the following molar ratios:
Chloride ferrous copper - 1,0
Chloride monovalent copper - 0,1
Magnesium oxide - 2,0
The reagent is conveniently prepared as follows: 1.1 mole of ferrous chloride copper dissolved in water to saturation. Add 2 mol of magnesium oxide. The mixture is evaporated to dryness and granularit. Then granulated product restore methane or hydrogen up until 0.1 mol of copper chloride will not be restored until chloride monovalent copper. When you regenerate the reagent should always be present chloride monovalent copper.Magnesium oxide is used to reduce the activity of the chloride of divalent copper. In combination with magnesium oxide it is possible to use other materials as diluent (aluminum oxide, silicon dioxide, fuller earth, and so on).When the conversion per cycle is limited to less than 20%, further chlorination of methane is limited to less than Elitny the catalyst is preferably prepared as follows: zeolite type A or type X (Kirk - Othmer Encyclopedia of chemical Technology, 3d Edition, vol. 15, p. 665) placed in a column, and a solution of soluble salts of magnesium (sulfate, nitrate, and so on) are passed through the zeolite, sodium is replaced by magnesium. The zeolite in the magnesium form then washed and dried and prepared for use. This method is well known (Kirk - Othmer Encyclopedia of chemical Technology, 3d Edition, vol. 13, p. 678, and so on).Although the previous illustration treated the chlorides of copper, such chlorides are not necessarily replaced by bromine. Methane can also be optionally replaced by ethane, propane or n-butane to obtain the corresponding alcohols.In an alternate implementation of the invention (Fig. 2) lowered fluidization 28 and fluidization 34, shown in Fig. 1. In Fig. 2 their equipment marked with the same numerals, and the index A is added for ease of comparison. The entire quantity of hydrochloric acid coming from fluidization 47A, completely absorbed in the reactor 19A without the formation of chlorine.A thorough thermodynamic analysis of reactions includes the following:
Constants of the reaction (T=300K):
2HCl+1/2 O2Cl2+ H2O F = -9080 feces K=9,35106;
2CuCl = 1/2 O2CuCl2+CuO F = - 15700 feces K=3,01 1011;
CuO + HCl CuCl2+ H2
Chloride ferrous copper - 1
The oxide of the divalent copper - 0,1
Chloride monovalent copper - 0,1
Magnesium oxide - 2
In Fig. 2 presents a simplified configuration of Fig. 1, where the lower alkane is converted into the corresponding lower alkanol according to the method described for Fig. 1, but with the addition of the oxide of the divalent metal, for example, oxide of divalent copper reagent 5.After the lower alkene, such as ethylene, processed on the same equipment in appropriate circumstances, his first glorious to 1,2-dichloroethane, and then hydrolyzing to ethylene glycol. The only difference is that require large portions of the pair to prevent condensation in the reactor 7A along with a higher temperature in fluidization 9A (135oC). The following are data depending>/BR>10 to 92.1
20 - 105,8
40 - 120,0
60 - 129,5
100 - 141,8
200 - 158,5
400 - 178,5
760 - 197,3
Thus, if the partial pressure of ethylene glycol is 80 mm RT.art., given the excess steam and excess ethylene, a temperature in fluidization 9A can be maintained at 135oC.After the ethylene alcohol is converted into pairs and similarly processed on the same equipment, it first glorious to ethylenchlorhydrine, which in turn hydrolyzing to ethylene glycol. Follow the same temperature precautions.As shown in Fig. 2, which depicts a typical continuous process using fluidized bed reactor, ethylene is served in fluidization 2A on 1A pipeline, where it interacts with ferrous chloride copper contained in the fluid reagent 5A consisting of a mixture of chloride of divalent copper, divalent oxide of copper, magnesium oxide and chloride of monovalent copper. Alternative instead of chlorides bromides are used.The reacted gas, consisting mainly of hydrochloric acid, 1,2-dichloroethane and excess ethylene, is fed via a pipe 3A in the cyclone 4A, from which pylera contains the catalyst 41A (magnesium zeolite), together with the steam, supplied by pipe 33A. The reacted gases containing ethylene glycol, hydrochloric acid and an excess of methane, leave the reactor 7A pipeline 8A, it turns them into fluidization 9A containing magnesium oxide 42A, which absorbs all of hydrochloric acid. Gases leaving fluidization 9A pipeline 10A in the cyclone 11A, from which dust particles are returned in fluidization 9A, contains a glycol, an excess of ethylene and water vapor. These gases are served by pipeline 12A in the capacitor 13A, where the glycol and water vapor are condensed and out of the condenser 13A pipeline 61A.Neskondensirovannyh ethylene leaves the condenser 13A pipeline 14A through the exhaust valve 17A and pipe 15A in the compressor 16A, which returns the excess ethylene in the pipe 1A.The spent reagent 5A of fluidization 2A is supplied through pipe 18A in fluidization 19A, where it meets a stream of gas consisting of air and hydrochloric acid; chloride monovalent copper is recycled back into the form of divalent copper. The regenerated reagent 20A flows through the pipe 21A, where she meets the transport gas (air) 22A, which raises his trubes cyclone 24A in fluidization 2A.Exhaust magnesium oxide 42A out of fluidization 9A pipeline 43A, he sends it in fluidization 47A, where it meets a stream of air introduced through the pipe 50A, which regenerates the spent magnesium oxide 48A. Generated magnesium oxide is fed via a pipe 51A, where she meets the transport gas (air) 52A, which raises it to the cyclone 54a pipeline 53A. Transport gas release pipe 55A, and the regenerated magnesium oxide goes cyclone 54A in fluidization 9A.Gases leaving fluidization 47A containing hydrochloric acid and air, come through the pipeline 44A in the cyclone 45A, where dust particles are returned in fluidization 47A, and the gas is sent through a pipe 46A in fluidization 19A.Air enters fluidized bed 47A pipeline 50A. Temperatures indicated in Fig. 2, are pointing. Reagent 5A contains an excess of copper oxide.Similarly receive propylene glycol from propylene. When the starting material to obtain ethylene glycol is ethyl alcohol instead of ethylene, the condensed alcohol, water and glycol obtained in the condenser 13A, served in a separator (not display The described method and equipment, thus, are useful for converting lower alkanes to corresponding lower alkanols, and for conversion of lower alkenes or lower alkanols to the corresponding glycols. Lower monobasic or dibasic alcohols obtained by the following steps:
a) interaction of the original product with a halide of the divalent metal (where the metal is in the higher of two possible valence States) to obtain a reaction product corresponding to the halide monovalent metal (where the metal is in the lower of the two possible valence States) and halogen acid;
b) interaction of the reaction product from stage (a) and halogen acids with magnesium oxide to obtain the corresponding lower monobasic or dibasic of alkanol;
where the initial product to receive the lower monobasic alcohol is a lower alkane from which to obtain the corresponding lower alkanol, and the source product to receive the lower dibasic alcohol is either low alkanol or lower alkene, of which receive the respective lower glycol. To carry out the necessary reactions predudices description. Obviously, in the process, systems and compositions can be made various changes within the scope and spirit of the invention or without losing its material advantages. Method, system and products described herein are merely illustrative for the preferred implementation of the invention. 1. The method of obtaining the lowest alkanol or lower glycol, wherein the initial product is subjected to interaction with the halide of the divalent copper at a temperature of about 300 to 360oC with obtaining the product of the reaction, the halide monovalent copper and halogen acids and the interaction of the obtained reaction product and halogen acids with magnesium oxide, to obtain the corresponding lower alkanol or lower glycol, where as the original product for a low alkanol use lower alkane, and as the source of the product to obtain the lowest glycol use low alkanol or lower alkene.2. The method according to p. 1 a low alkanol from the corresponding lower alkane, characterized in that it includes a) the interaction of the lower alkane with the halide of the divalent copper to obtain the corresponding lower alkyla alkylhalogenide and halogen acids with magnesium oxide to obtain the corresponding lower alkanol and hydrate of magnesium halide.3. The method according to p. 2, characterized in that it further includes (C) interaction of halide monovalent copper with a halogen acid and oxygen to produce the halide of the divalent copper, and (d) conversion of the hydrate of the halide of magnesium in magnesium oxide and halogen acid.4. The method according to p. 3, wherein the copper halide is copper chloride.5. The method according to p. 4, characterized in that it is carried out in the fluidized bed.6. The method according to p. 1 production of methanol from methane, characterized in that it includes a) the interaction of methane and chloride divalent copper to obtain methyl chloride, chloride of monovalent copper and hydrochloric acid, (b) deletion of methyl chloride and hydrochloric acid, obtained in stage (a), together with the steam through magnesium zeolite catalyst to obtain methyl alcohol and hydrochloric acid, (C) interaction of methyl alcohol and hydrochloric acid, obtained in stage (b), with magnesium oxide to obtain methyl alcohol and hydrate of magnesium chloride and (d) the conversion of the hydrate of magnesium chloride to magnesium oxide and hydrochloric acid.7. The method according to p. 6, characterized in that his conduct is lorida divalent copper in the fluidized bed, comprising a mixture of magnesium oxide, ferrous chloride and copper chloride monovalent copper, to obtain the composition of gases containing hydrochloric acid, methyl chloride and unreacted methane, (b) transmittance of the composition of gases and steam through magnesium zeolite catalyst to obtain a mixture of methyl alcohol, hydrochloric acid and methane, (C) passing the mixture through a fluidized bed containing magnesium oxide which adsorbs all of hydrochloric acid, (d) condensation of methyl alcohol from the remaining mixture of methyl alcohol and methane and (e) recycling of methane to the step (a).9. The method according to p. 1 obtain glycol from the corresponding alkene or alkanol, wherein the stage includes a) interaction alkene and alkanol with the halide of the divalent copper with getting alkylhalogenide or galagedera, halide monovalent copper and halogen acids and (b) the interaction of the obtained alkylhalogenide or galagedera and halogen acids with magnesium oxide to obtain the corresponding glycol and hydrate of magnesium halide.10. Fluidized bed to convert methane to methanol, characterized in that it includes the respectively.11. Fluidized bed under item 10, characterized in that it further comprises a 0.1 mol of oxide of divalent copper.12. System fluidized bed to convert methane to methanol, characterized in that it comprises a) a reactor with a fluidized bed containing as a reactant a fluidized bed comprising a mixture of CuCl2, CuCl and MgO, means for supplying methane to the reactor with him the fluidized bed and the pipeline is designed for removal of unreacted methane and the resulting gases from the reactor in (b), (b) a reactor containing a catalyst comprising a magnesium zeolite, means to supply steam into the pipeline designed to supply the mixture through contained in the catalyst, and the second pipeline is designed to supply unreacted methane and reaction products in (C), (C) the first fluidization containing the adsorbent is magnesium oxide to absorb the hydrochloric acid and a third pipe for supplying the remaining gaseous components of the specified fluidization in (d), and (d) the condenser is designed to condense methanol, and the fourth pipeline to return unreacted methanol in the reactor pelino contains (e) a second fluidization, means for feeding the spent reagent from the reactor fluidized bed in the second fluidization, means to supply air and hydrochloric acid in the second fluidization and through which it spent reagent for regeneration of spent reagent, means for feeding the regenerated reactant in a reactor with a fluidized bed and the fifth pipeline for gas supply from the second fluidization in (f), and (f) the third fluidization, which contains an adsorbent for the adsorption of all traces of hydrochloric acid in the gases withdrawn from the second fluidization, and means for releasing the exhaust of clean gas.14. System fluidized bed under item 13, characterized in that it further comprises (g) a fourth fluidization, a pipeline for supplying the spent adsorbent their third fluidization in the fourth, piping for air supply in the fourth fluidization and through the spent adsorbent in it for the regeneration of the specified adsorbent, means for transporting the regenerated adsorbent in the third fluidization and piping for the exhaust gases in the second fluidization.15. System fluidized bed under item 14, characterized TA from the first fluidization in the fifth, means for supplying air into the fifth fluidization through the spent adsorbent in it, for the regeneration of the specified adsorbent, means for transporting the regenerated adsorbent in the first fluidization and means for supplying gases emitted from him, in the second fluidization.Priority points:
04.11.92 on PP.2 - 8;
04.08.93 on PP.1, 9 and 11.
FIELD: petrochemical process catalysts.
SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.
EFFECT: increased yield of lower olefins.
3 cl, 2 tbl, 18 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).
EFFECT: increased mechanical strength and wear resistance of catalyst.