NOVEL TRIALUMINUM HYDROXY CHLORIDE OF FORMULA AL3(OH)4CL5 AND PROCESS FOR THE PREPARATION THEREOF FROM INDUSTRIAL WASTE

Abstract

The present invention relates to novel Tri Aluminum Hydroxy chloride of the formula Al.sub.3(OH).sub.4Cl.sub.5. The present invention also relates to a process for the preparation of Tri Aluminum Hydroxy chloride of the formula Al.sub.3(OH).sub.4Cl.sub.5 from industrial waste wherein the industrial waste is obtained from the chemical reactions, the reactions using anhydrous aluminum chloride as acid catalyst, for example Friedel-Craft reactions. The product of the formula Al.sub.3(OH).sub.4Cl.sub.5 is obtained in an aqueous solution form from the industrial waste.

Claims

1. A monomer compound Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5.

2. A compound of formula Al.sub.3(OH).sub.4Cl.sub.5 as claimed in claim-1 is obtained as aqueous solution.

3. A compound of formula Al.sub.3(OH).sub.4Cl.sub.5 as claimed in claim-2 wherein quantity of Al.sub.3(OH).sub.4Cl.sub.5 in water is between 9% to 30%.

4. The process for the preparation of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5 from industrial waste obtained from aluminium chloride aided friedel-craft reactions, the process comprises: i. diluting spent aluminium chloride solution with addition of water into it; ii. reacting step-i with aluminium hydroxide or alumina and base at a temperature between 25 C. to 40 C.; iii. Stirred the reaction mixture between 25 C. to 40 C. till get the clear solution; iv. optionally adding iron scrap into the above mixture under stirring at a temperature between 25 C. to 40 C.; v. filtering the reaction mixture & washing it with water to get the aqueous solution of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5.

5. The process as claimed in claim-4 wherein the ratio of moist AlCl.sub.3 in industrial waste is between 10% to 30%.

6. The process as claimed in claim-4 wherein the quantity of Al(OH).sub.3 or Alumina is between 0.03% to 0.05%.

7. The process as claimed in claim-4 wherein base is selected from metal hydroxides, metal carbonates, metal bicarbonates or combination thereof.

8. The process as claimed in claim-4 wherein the quantity of base is between 5% to 10%.

9. The process as claimed in claim-4 wherein the quantity of water for diluting spent is between 1% to 5%.

10. The process as claimed in claim-4 wherein if spent AlCl.sub.3 is taken from CPC green industrial waste, Copper powder is obtained as byproduct.

11. The process as claimed in claim-4 wherein the quantity of Al.sub.3(OH).sub.4Cl.sub.5 in water is between 9% to 30%.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0024] FIG. 1 is a flow-diagram for the preparation of Tri Aluminum Hydroxy chloride from industrial waste obtained from friedel-craft reactions other than CPC green manufacturing.

[0025] FIG. 2 is a flow-diagram for the preparation of Tri Aluminum Hydroxy chloride from industrial waste obtained from CPC green manufacturing industries.

DETAILED DESCRIPTION OF THE INVENTION

[0026] Thus, the present invention is directed to a novel compound Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5. Further, the present invention is also directed to a process for the preparation of compound of formula Al.sub.3(OH).sub.4Cl.sub.5 from industrial waste obtained from aluminium chloride (AlCl.sub.3) aided friedel-craft reactions.

[0027] Tri Aluminum Hydroxy Chloride monomer of formula Al.sub.3(OH).sub.4Cl.sub.5 is also known as Aluminum Hydroxide Chloride (AHC), Tri Aluminum Tetra Hydroxyl Penta Chloride, Basic Aluminum Chloride, Aluminum Penta Chloro Hydroxide, or Aluminum Tetrahydroxy Chloride. Aluminium chloride is used as lewis acid catalyst in the friedel-craft reactions, such reactions are used in manufacture of dyes and dyes intermediates, bulk drug or active pharmaceutical ingredients, chemicals and their intermediates for example but not limited to m-phenoxybenzaldehyde, acetyl yarayara, 2,4,6-Trimethyl Benzoyl Chloride, phthalocynine green, copper phthalocynine green-7, pentamethylindane, alfa-dimethyl phenyl acetic acid methyl ester.

[0028] The industrial waste obtained from the friedel-craft reactions is highly acidic and also called as spent aluminium chloride solution as spent mainly contains aluminium chloride. Apart from Aluminum chloride, there are also heavy metals such as mercury, cadmium, arsenic, lead, iron, zinc, copper, chromium, manganese present in spent. Further, industrial waste also contains unreacted raw materials, starting materials or impurities formed during the reaction.

[0029] According to the first aspect, there is provided a monomer compound of formula Al.sub.3(OH).sub.4Cl.sub.5.

[0030] Preferably, the compound of formula Al.sub.3(OH).sub.4Cl.sub.5 is obtained in aqueous solution.

[0031] According to the second aspect, there is provided a process for the preparation of compound of formula Al.sub.3(OH).sub.4Cl.sub.5 from industrial waste.

[0032] A process for the preparation of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5 from industrial waste obtained from aluminium chloride aided friedel-craft reactions, the process comprises: [0033] (i) diluting spent aluminium chloride solution with addition of water into it; [0034] (ii) reacting step-i with aluminium hydroxide or alumina and base at a temperature between 25 C. to 40 C.; [0035] (iii) Stirred the reaction mixture between 25 C. to 40 C. till get the clear solution; [0036] (iv) optionally adding iron scrap into the above mixture under stirring at a temperature between 25 C. to 40 C.; [0037] (v) filtering the reaction mixture & washing it with water to get the aqueous solution of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5.

[0038] Spent obtained after the completion of friedel-craft reaction is acidic in nature and it mainly contains moist aluminium chloride, calcium chloride, sodium chloride as V-salt, heavy metals and unreacted organic compounds used in the reaction.

[0039] Moist aluminium chloride ratio in the spent is between 10% to 30% while moisture in the spent may varied between 70% to 90%.

[0040] The presence of the other salts such as calcium chloride and sodium chloride as V-salt depend on the friedel-craft reaction taken place, the sum of the total quantity of calcium chloride and sodium chloride may be varied between 3% to 30%.

[0041] Total heavy metals present in the spent depend on the catalyst, raw materials, starting materials or the combination thereof used in the friedel-craft reaction. In general and preferably, spent contains heavy metals such as but not limited to mercury, cadmium, arsenic, lead, iron, zinc, copper, chromium, manganese and the sum of quantity of all heavy metals is varied between 1-1000 mg/kg.

[0042] In case of CPC green manufacturing, cuprous chloride (CuCl.sub.3) is used in the reaction hence spent or industrial waste also contains copper as the second major ingredient which if desirous, may be isolated as bi-product during the preparation of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5.

[0043] FIG. 1 has shown a flow-diagram for the preparation of Aluminum Hydroxide chloride from industrial waste obtained from friedel-craft reactions other than CPC green manufacturing.

[0044] FIG. 2 has shown a flow-diagram for the preparation of Tri Aluminum Hydroxy chloride from industrial waste obtained from CPC green manufacturing industries.

[0045] A process for the preparation of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5 may now be described as follows:

[0046] Spent aluminium chloride solution obtained from friedel-craft reaction is taken for preparation of aqueous Tri Aluminum Hydroxy chloride solution.

[0047] Accordingly, In a reactor, a certain amount of water is added into spent aluminium chloride solution and stirred at a temperature between 25 C. to 40 C. Alumina (Al.sub.2O.sub.3) or Aluminium hydroxide (Al(OH).sub.3) is added into the above precursor/mixture under stirring.

[0048] At least one base is added into the said mixture and stirred till the precursor/mixture turned into the clear solution. Addition of the base make the reaction exothermic hence while adding the base into the mixture, it is required to control the temperature of the reaction between 25 C. to 40 C. using the methods known in the art. Once the clear solution is obtained, calcium hydroxide (Ca(OH).sub.2) is added into it and stirred at the same temperature for half an hour. The mixture then taken for nutch filtration using filter press. The solution contains Tri Aluminum Hydroxy chloride product of formula Al.sub.3(OH).sub.4Cl.sub.5.

[0049] Reaction equation for preparation of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5 is provided as follows:

4Al(OH).sub.3+5AlCl.sub.3.fwdarw.3Al.sub.3(OH).sub.4Cl.sub.5

OR

3AlCl.sub.3+Ca(OH).sub.2+2NaOH.fwdarw.Al.sub.3(OH).sub.4Cl.sub.5+CaCl.sub.2+2NaCl

[0050] The aqueous solution of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5 thus obtained, contains Tri Aluminum Hydroxy chloride quantity between 9% to 30% w/v.

[0051] In case of CPC green manufacturing, cuprous chloride (CuCl.sub.3) is used in the friedel-craft reaction hence spent or industrial waste also contains copper as the second major ingredient. While using CPC green spent instead of the above spent, optionally iron ore is added in the reaction mixture and copper may be isolated as bi-product during the preparation of Tri Aluminum Hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5.

[0052] The amount or ratio of the raw materials/water/reactants used in the reaction to obtain 1 kg of finished Al.sub.3(OH).sub.4Cl.sub.5 solution is provided as follows:

[0053] Spent Aluminium chloride solution: between 85% to 95% compare to the finished Al.sub.3(OH).sub.4Cl.sub.5 solution.

[0054] Alumina (Al.sub.2O.sub.3)/Aluminum Hydroxide {Al(OH).sub.3}: 0.03% to 0.05%

[0055] Water: between 1% to 5%

[0056] Base: between 5% to 10%

[0057] Base is selected from metal hydroxides, metal carbonates, metal bicarbonates or combination thereof for example but not limited to NaOH, Na.sub.2Co.sub.3, Ca(OH).sub.2, NaHCO.sub.3 etc.

[0058] The quantities mentioned above is taken based on the preparation of 1 kg finished Al.sub.3(OH).sub.4Cl.sub.5 solution. Further, it is also possible to commercialize and mass produce the finished Al.sub.3(OH).sub.4Cl.sub.5 solution by calculating the ratio of each material/chemical provided above.

[0059] Analysis of the process for the preparation of Tri Aluminium hydroxy chloride of formula Al.sub.3(OH).sub.4Cl.sub.5 is done using the analytical methods such as Atomic absorption spectrophotometer, ion chromatograph while identification of Organic Impurities done by Gas Chromatograph MS.

[0060] The present invention demonstrated examples cited below, which are provided as illustration only and therefore should not be construed as limitation of the possible and future invention.

[0061] Analysis of the Spent and Finished Product:

[0062] All the raw materials, Spent AlCl.sub.3 obtained from the industry, finished Al.sub.3(OH).sub.4Cl.sub.5 solution sent for analysis at Pollucon Laboratories Pvt. Ltd.

[0063] Below Results i.e. (i) before process & (ii) after process for each experimental example are obtained from the samples sent to Pollucon Laboratories Pvt. Ltd, Surat, Gujarat, India.

[0064] Pollucon Laboratories Pvt. Ltd. is recognized by MOEE, New Delhi under section 12 of Environmental Protection Act-1986 and acting as environmental auditors, consultants & analysts.

EXAMPLES OF THE INVENTION: PROCESS FOR THE PREPARATION OF TRI ALUMINUM HYDROXY CHLORIDE OF FORMULA Al.SUB.3.(OH).SUB.4.Cl.SUB.5

Example-1: From Spent Aluminum Chloride Solution Generated from AcetylYaraYara Manufacturing

[0065] Before the Process: Characteristics of Spent Aluminium Chloride Solution:

TABLE-US-00001 Present in Spent/ Sr. Industrial No. Parameters Unit Waste 1 Moisture % 69.19 2 Aluminium Chloride % 28.18 as AICI.sub.3 3 HCL@ % 1.40 4 V-salt (Sodium Chloride) % 1.20 Heavy Metals 5 Mercury as Hg mg/kg <0.1 6 Arsenic as As mg/kg <0.1 7 Cadmium as Cd mg/kg 0.06 8 Lead as Pb mg/kg 0.39 9 Iron as Fe mg/kg 6.6 10 Zinc as Zn mg/kg 0.57 11 Copper as Cu mg/kg 0.68 12 Chromium as Cr mg/kg 0.45 13 Manganese as Mn mg/kg 0.58 Organic Compound 14 Nitro benzene mg/kg 10.8 15 2- mithoxy naphthalene mg/kg 0.67 16 2 acetyl 6 mg/kg 53.55 methoxyNepthelene 17 Acetyl Chloride mg/kg 4.1 @HCI (based on remaining chlorine after deduction from total chlorine)

[0066] After the Process: Characteristics of Tri Aluminium Hydroxy Chloride Solution:

TABLE-US-00002 In Aluminium Sr. Hydroxide No. Parameters Unit Chloride 1 Moisture % 67.20 2 Aluminium % 22.72 Hydroxide Chloride 3 HCL@ % <0.01 4 V-salt (as Sodium Chloride) % 5.20 5 Calcium Chloride % 4.80 Heavy Metals 6 Mercury as Hg mg/kg <0.1 7 Arsenic as As mg/kg <0.1 8 Cadmium as Cd mg/kg 0.04 9 Lead as Pb mg/kg 0.13 10 Iron as Fe mg/kg 0.3 11 Zinc as Zn mg/kg 0.23 12 Copper as Cu mg/kg 0.12 13 Chromium as Cr mg/kg 0.19 14 Manganese as Mn mg/kg 0.02 Organic Compound 15 Nitro benzene mg/kg 5.73 16 2- mithoxy naphthalene mg/kg 0.03 17 2 acetyl 6 methoxy mg/kg 4.84 Nepthelene 18 Acetyl Chloride mg/kg 3.2 @HCI (based on remaining chlorine after deduction from total chlorine)

Example-2: From Spent Aluminum Chloride Solution Generated from Fex-10 (4-(Cyclopropyl-Oxo-Methyl)-Alpha,Alpha Dimethyl Phenyl Ethyl Acetate Manufacturing Industries

[0067] Before the Process: Characteristics of Spent Aluminium Chloride Solution:

TABLE-US-00003 Present in Spent/ Sr. Industrial No. Parameters Unit Waste 1 Moisture % 76.33 2 Aluminium Chloride % 21.70 as AICI.sub.3 3 HCL@ % 1.10 4 V-salt (as Sodium Chloride) % 0.40 Heavy Metals 5 Mercury as Hg mg/kg <0.1 6 Arsenic as As mg/kg <0.1 7 Cadmium as Cd mg/kg 0.01 8 Lead as Pb mg/kg 8.29 9 Iron as Fe mg/kg 38.48 10 Zinc as Zn mg/kg 6.98 11 Copper as Cu mg/kg 3.48 12 Chromium as Cr mg/kg 1.52 13 Manganese as Mn mg/kg 9.20 Organic Compound 14 Benzene mg/kg 0.02 15 2- methyl prop 2 ethyl mg/kg 1.01 acetate 16 Methylene Chloride mg/kg 18.5 17 2,2- dimethyl phenyl ethyl mg/kg 1.06 acetae 18 4, chlorobutyl chloride mg/kg <0.1 @HCI (based on remaining chlorine after deduction from total chlorine)

[0068] After Process: Characteristics of Tri Aluminum Hydroxy Chloride as Finished Product:

TABLE-US-00004 In Aluminium Sr. Hydroxide No. Parameters Unit Chloride 1 Moisture % 71.80 2 Aluminium % 17.70 Hydroxide Chloride 3 HCL@ % <0.01 4 V-salt (as Sodium Chloride) % 5.14 5 Calcium Chloride % 5.28 Heavy Metals 6 Mercury as Hg mg/kg <0.1 7 Arsenic as As mg/kg <0.1 8 Cadmium as Cd mg/kg 0.005 9 Lead as Pb mg/kg 3.84 10 Iron as Fe mg/kg 26.91 11 Zinc as Zn mg/kg 5.21 12 Copper as Cu mg/kg 2.78 13 Chromium as Cr mg/kg 0.99 14 Manganese as Mn mg/kg 7.90 Organic Compound 14 Benzene mg/kg <0.1 15 2- methyl prop 2 ethyl mg/kg 0.43 acetate 16 Methylene Chloride mg/kg 12.5 17 2,2- dimethyl phenyl mg/kg 0.85 ethyl acetae 18 4, chlorobutyl chloride mg/kg <0.1 @HCI (based on remaining chlorine after deduction from total chlorine)

Example-3: From Spent Aluminum Chloride Solution Generated from Penta Methyl Indane (Intermediate Stage) Manufacturing Industries

[0069] Before the Process: Characteristics of Spent Aluminium Chloride Solution:

TABLE-US-00005 Present in Spent/ Sr. Industrial No. Parameters Unit Waste 1 Moisture % 69.40 2 Aluminium Chloride % 28.70 as AICI.sub.3 3 HCL.sup.@ % 1.80 4 V-salt (as Sodium Chloride) % 0.04 Heavy Metals 5 Mercury as Hg mg/kg <0.1 6 Arsenic as As mg/kg <0.1 7 Cadmium as Cd mg/kg 0.08 8 Lead as Pb mg/kg 0.75 9 Iron as Fe mg/kg 6.20 10 Zinc as Zn mg/kg 1.06 11 Copper as Cu mg/kg 1.04 12 Chromium as Cr mg/kg 0.81 13 Manganese as Mn mg/kg 0.78 Organic Compound 14 Propeleneoxide mg/kg <0.1 15 Di chloromethane mg/kg 0.021 @HCI (based on remaining chlorine after deduction from total chlorine)

[0070] After the Process: Characteristics of Tri Aluminum Hydroxy Chloride as Finished Product:

TABLE-US-00006 In Aluminium Sr. Hydroxide No. Parameters Unit Chloride 1 Moisture % 66.4 2 Aluminium % 23.20 Hydroxide Chloride 3 HCL@ % <0.01 4 V-salt (as Sodium Chloride) % 5.30 5 Calcium Chloride % 4.90 Heavy Metals 6 Mercury as Hg mg/kg <0.1 7 Arsenic as As mg/kg <0.1 8 Cadmium as Cd mg/kg 0.04 9 Lead as Pb mg/kg 0.37 10 Iron as Fe mg/kg 3.0 11 Zinc as Zn mg/kg 0.46 12 Copper as Cu mg/kg 0.29 13 Chromium as Cr mg/kg 0.19 14 Manganese as Mn mg/kg 0.06 Organic Compound 15 Propeleneoxide mg/kg <0.1 16 Di chloromethane mg/kg 0.007 @HCI (based on remaining chlorine after deduction from total chlorine)

Example-4: From Spent Aluminum Chloride Solution Generated from CPC Green Manufacturing Industries

[0071] Before Process: Characteristics of Spent Aluminium Chloride Solution:

TABLE-US-00007 Present in Spent/ Sr. Industrial No. Parameters Unit Waste 1 Moisture % 84.10 2 Aluminium Chloride % 11.52 as AICI.sub.3 3 HCL@ % 1.60 4 V-salt (as Sodium Chloride) % 1.40 5 Cuppers Chloride as % 0.614 CuCl.sub.3 Heavy Metals 6 Mercury as Hg mg/kg <0.1 7 Arsenic as As mg/kg <0.1 8 Cadmium as Cd mg/kg 0.12 9 Lead as Pb mg/kg 4.90 10 Iron as Fe mg/kg 1947 11 Zinc as Zn mg/kg 29.53 12 Copper as Cu mg/kg 2296 13 Chromium as Cr mg/kg 1.09 14 Manganese as Mn mg/kg 19.22 15 Ferric Chloride mg/kg 5654 Organic Compound 16 CPC- Blue mg/kg 7.40 17 CPC- Green mg/kg 8.80 @HCI (based on remaining chlorine after deduction from total chlorine)

[0072] After the Process: Characteristics of Tri Aluminum Hydroxy Chloride as Finished Product:

TABLE-US-00008 In Aluminium Sr. Hydroxide No. Parameters Unit Chloride 1 Moisture % 79.90 2 Aluminium % 9.30 Hydroxide Chloride 3 HCL@ % <0.01 4 V-salt (as Sodium Chloride) % 5.4 5 Calcium Chloride % 4.8 6 Cuppers Chloride as % 123 CuCl.sub.3 Heavy Metals 7 Mercury as Hg mg/kg <0.1 8 Arsenic as As mg/kg <0.1 9 Cadmium as Cd mg/kg 0.086 10 Lead as Pb mg/kg 3.1 11 Iron as Fe mg/kg 84.42 12 Zinc as Zn mg/kg 36.8 13 Copper as Cu mg/kg 46.04 14 Chromium as Cr mg/kg 0.82 15 Manganese as Mn mg/kg 8.19 16 Ferric Chloride mg/kg 245 Organic Compound 17 CPC- Blue mg/kg <5 18 CPC- Green mg/kg <5 @HCI (based on remaining chlorine after deduction from total chlorine)

[0073] Copper as Bi-Product from CPC Green Spent:

TABLE-US-00009 Sr. Result No. Parameters (%) 1 Moisture (By KF) 9.00 2 Copper as Cu 88.40 3 Fe.sub.2O.sub.3 2.60

[0074] While the invention has been described and exemplified in sufficient detail for those skilled in this art to make and use it, various alternatives, modifications, and improvements should be apparent without departing from the spirit and scope of the invention.

[0075] One skilled in the art readily appreciates that the present invention is well adapted to carry out the objects and obtain the ends and advantages mentioned, as well as those inherent therein. It will be readily apparent to a person skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit of the invention.

[0076] All patents and publications mentioned in the specification are indicative of the levels of those of ordinary skill in the art to which the invention pertains. All patents and publications are herein incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.

[0077] The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations, which are not specifically disclosed herein. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

[0078] Other embodiments are set forth within the following claims.