FORM 2
THE PATENTS ACT, 1970
(39 OF 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
A PROCESS FOR THE REMOVAL OF METAL CONTAMINANTS
FROM FLUIDS
RELIANCE INDUSTRIES LIMITED
an Indian organization
of 3rd Floor, Maker Chamber-IV
222, Nariman Point, Mumbai-400021,
Maharashtra, India.
Inventors:
1. KUMAR PRAKASH
2. PURANIK VIJAYALAKSHMI RAVI
3. GOPAL KRISHNAN KALPANA
4. PATIL MALLIKARJUN B.
5. JASRA RAKSH VIR
THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED.
■

FIELD OF THE DISCLOSURE
The present disclosure relates to a process for the removal of metal contaminants from fluids.
BACKGROUND
Chlorinated polymers find extensive applications in roofing membranes, geomembranes, coated fabrics, cable insulation and as impact modifiers and base polymers. Their excellent physical and mechanical properties such as resistance to chemicals and oils, flame retardancy, tensile strength and resistance to abrasion have resulted in their enormous industrial popularity and applicability.
Chlorinated polymers are usually prepared by reacting chlorine free polymers and/ or copolymers with chlorinating agents, at pre-determined temperature and pressure conditions. Ethylene and hydrochloric acid are the commonly used raw materials in the polymerization processes. However, due to the highly corrosive nature of the above-mentioned chemicals, more specifically in the presence of water, numerous incidences of corrosion of reaction vessels and pipelines are observed. Furthermore, the corroded surfaces give off metallic particulate matter that enters the polymerization reaction via the raw materials. Presence of metal contaminants in the reaction leads to a pressure drop in the system along with generation of hot spots in the downstream catalyst bed leading to reduction

in the life of the catalyst. Even further, fouling of the catalyst results, which creates unwanted products in the reaction, leading to a decrease in the overall
yield.
Different methods have been developed to eliminate the metal contaminants from the raw materials. EP 0618170 discloses a strong basic anion exchange resin for removing iron impurities from hydrochloric acid. EP 0725759 discloses filtration and ion exchange techniques for removing coloring material such as iron and halogen from hydrochloric acid. The method of EP 0725759 further includes a step of addition of a reducing agent in the hydrochloric acid, post the removal of the coloring matter. US 3411879 discloses a process for the removal of fluoride ions from aqueous hydrochloric acid by treating it with a treating agent such as activated alumina or silica gel. US 5330735 reveals a process for treating contaminated hydrochloric acid to remove silicone containing materials that may act as impurities such as silane, silanol and siloxane. The process of US 5330735 uses a hydrophobic polystyrenic resin. Although there has been significant development in the techniques for the removal of metal contaminants from raw materials, the conventional methods are still accompanied by certain disadvantages such as inability to remove metal contaminants below certain sizes and use of expensive reagents and substrates. US 8298311 and EP 0630677 disclose ceramic articles for the purposes of filtration and removal of impurities such as dust. However, the afore-mentioned

prior art methods remain silent on use of ceramic materials for removing metal contaminants.
The inventors of the present disclosure have envisaged a simple and economic process for the removal of metal contaminants from the raw materials of the polymerization process.
OBJECTS
Some of the objects of the present disclosure which at least one embodiment
herein satisfies are as follows:
It is an object of the present disclosure to provide a process for the removal of
metal contaminants from a fluid stream.
It is another object of the present disclosure to provide a simple and cost
effective process for the removal of metal contaminants from a fluid stream.
It is yet another object of the present disclosure to provide an environment
friendly process for the removal of metal contaminants from a fluid stream.
It is even further an object of the present disclosure to ameliorate one or more
problems of the prior art or to at least provide a useful alternative.
Other objects and advantages of the present disclosure will be more apparent
from the following description which is not intended to limit the scope of the
present disclosure.

SUMMARY
The present disclosure provides a process for obtaining a fluid stream substantially free of metal contaminants, characterized in that the metal content of said stream being less than 50 ppm; said process comprising the following steps:
i. providing a fluid stream contaminated with at least one metal contaminant; said stream being selected from the group consisting of a stream of mineral acid(s) and a stream of alkylene(s), said metal contaminant is at least one selected from the group consisting of elemental metals and metal oxides; and
ii. contacting said stream with macroporos alpha alumina in order to trap said metal contaminants, thereby providing a fluid stream free of metal contaminants and spent macroporos alpha alumina.
Typically, the process further comprising a step of regenerating said spent macroporos alpha alumina by washing said spent macroporos alpha alumina with at least one purified stream selected from the group consisting of a stream of mineral acid(s) and a stream of alkylene(s).

Typically, said mineral acid is at least one corrosive acid selected from the
group consisting of hydrochloric acid, hydrofluoric acid, hydrobromic acid,
nitric acid, phosphoric acid, sulfuric acid, boric acid and perchloric acid.
Typically, said fluid stream is a hydrochloric acid stream.
Typically, said alkylene is at least one selected from the group consisting of
ethylene, methylene and propylene.
Typically, said fluid stream is an ethylene stream.
Typically, said metal contaminant is selected from the group consisting of iron,
nickel, copper, chromium, lead, zinc, manganese and oxides thereof.
Typically, said metal contaminant is iron oxide.
Typically, said step of contacting is carried out at a temperature ranging
between 20 °C and 200 °C.
Typically, said step of contacting is carried out at a pressure ranging between 1
kg/ cm and 10 kg/ cm .
Typically, said step of contacting is carried out at a gas hourly space velocity
(GHSV) ranging between 10,000 per hour and 20,000 per hour.
Typically, the shape of said macroporos alpha alumina is selected from the
group of shapes consisting of bead shape and disc shape.

DETAILED DESCRIPTION
The present disclosure provides a process for obtaining a fluid stream, substantially free of metal contaminants, that is capable of being used as a raw material in the process of preparation of chlorinated polymers. The process of polymerization becomes more cost effective, environment friendly and high yielding by using the purified raw material streams provided by the process of the present disclosure. Typically, the fluid stream, substantially free of metal contaminants, is characterized in that the metal content of the stream is less than 50 ppm.
The process of obtaining a fluid stream substantially free of metal contaminants comprises an initial step of providing a fluid stream contaminated with at least one metal contaminant. Typically, the fluid stream is selected from the group consisting of a stream of mineral acid(s) and a stream of alkylene(s). The mineral acid used in the present disclosure is at least one corrosive acid selected from the group that includes but is not limited to hydrochloric acid, hydrofluoric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid and perchloric acid. Further, the alkylene used in the present disclosure includes but is not limited to ethylene, methylene and propylene. The metal contaminant contained in the fluid stream includes but is not limited to elemental metal(s) and metal oxide(s). Typically, the metal contaminant used in the present

disclosure is selected from the group consisting of iron, nickel, copper, chromium, lead, zinc, manganese and oxides thereof.
The next step involves contacting the above-mentioned fluid stream with macroporos alpha alumina in order to trap the afore-stated metal contaminants. Macroporos alpha alumina typically withstands a highly acidic and corrosive environment for prolonged periods. Therefore, its use as a molecular sieve is highly effective in the process of the present disclosure. In one embodiment, macroporos alpha alumina with characteristic morphology and integrity is obtained when the precursor gamma alumina is subjected to heat treatment at a temperature ranging between 1500 °C and 1700 °C. The shape of macroporos alpha alumina is selected from the group of shapes consisting of bead shape and disc shape. The step of contacting is carried out at a temperature ranging between 20 °C and 200 °C and at a pressure ranging between 1 kg/ cm and 10 kg/ cm2. Typically, the gas hourly space velocity (GHSV) of the fluid stream ranges between 10,000 per hour and 20,000 per hour.
The process of the present disclosure removes the metal contaminants by shape selectivity. This feature is characteristic to the process of the present disclosure. The step of contacting provides a fluid stream free of metal contaminants and spent macroporos alpha alumina. The spent macroporos alpha alumina of the present disclosure may further be regenerated by washing with at least one

purified stream selected from the group consisting of a stream of mineral acid(s) and a stream of alkylene(s). The mineral acid of the present disclosure is at least one corrosive acid that includes but is not limited to hydrochloric acid, hydrofluoric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid and perchloric acid and the alkylene is at least one selected from the group consisting of ethylene, methylene and propylene.
In one embodiment of the present disclosure, hydrochloric acid vapors, substantially free of iron oxide contaminants, are obtained by passing the dry hydrochloric acid vapors containing iron oxide contaminants, through a fixed bed containing macroporos alpha alumina.
In another embodiment of the present disclosure, an ethylene stream, substantially free of iron oxide contaminants, is obtained by passing the ethylene stream containing iron oxide contaminants, through a fixed bed containing macroporos alpha alumina.
The present disclosure will now be explained with the help of the following non-limiting examples:
Example 1: Removing meal contamination from a HC1 stream
300 g of porous alpha alumina was charged in an adsorbent column trap comprising SS316 and was activated at 200°C for 4 hours under air flow. A dry

hydrochloric acid stream was then passed through the column at 160 °C, at a flow rate of 1 liter per minute for 24 hours. The outlet stream emerging from the bed was analyzed for Fe content at the end of 24 hours. Presence of Fe in the outlet stream was analyzed by scrubbing the stream in deionized water. After scrubbing, the deionized water turned light yellow in color. The outlet stream-scrubbed deionized water was then subjected to Inductively Coupled Plasma Optical Emission spectrometer (ICP-OES) analysis which showed 38 ppm of Fe present in the free HC1.
Determination of the Fe content: The dry HC1, at 160 °C, obtained from a Vinyl Chloride Monomer (VCM) plant was analyzed for Fe contamination. The out-coming hydrochloric acid stream was analyzed by scrubbing the stream in deionized water for about 15 minutes. The scrubber was made by filling 50 ml of double distilled water in a glass trap. After scrubbing, the deionized water turned light yellow in color and was further subjected to ICP-OES analysis. The ICP analysis showed 38 ppm of iron present in the outlet stream as compared to the 600 ppm of iron present in a stream not subjected to porous alpha alumina adsorption.
Example 2: Removing meal contamination from an ethylene stream
Experiment no. 1 was repeated, however, instead of a hydrochloric acid stream, an ethylene stream emerging from a VCM plant was passed over an adsorption

column containing 86 g of porous alpha alumina at a flow rate of 500 ml/minute. The iron content of the outlet stream, post alumina adsorption, was found to be 46 ppm as compared to the 394 ppm Fe present without the outlet stream undergoing adsorption.
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
The foregoing description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments

herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
TECHNICAL ADVANTAGES
The present disclosure that relates to a process for the removal of metal
contaminants from a fluid stream has the following technical advantages:
The process of the present disclosure eliminates the phenomenon of catalyst
poisoning during the manufacture of chlorinated polymers.
Further, the process of the present disclosure is capable of removing iron oxide
contaminants of small sizes that cannot be removed by the prior art methods.
Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression "at least" or "at least one" suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the invention to achieve one or more of the desired objects or results.

The numerical values given for various physical parameters, dimensions and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention and the claims unless there is a statement in the specification to the contrary.
While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications in the process or compound or formulation or combination of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the invention.

We Claim:
1. A process for obtaining a fluid stream substantially free of metal
contaminants, characterized in that the metal content of said stream being
less than 50 ppm; said process comprising the following steps:
i. providing a fluid stream contaminated with at least one metal contaminant; said stream being selected from the group consisting of a stream of mineral acid(s) and a stream of alkylene(s), said metal contaminant is at least one selected from the group consisting of elemental metals and metal oxides; and
ii. contacting said stream with macroporos alpha alumina in order to trap said metal contaminants, thereby providing a fluid stream free of metal contaminants and spent macroporos alpha alumina.
2. The process as claimed in claim 1 further comprising a step of regenerating said spent macroporos alpha alumina by washing said spent macroporos alpha alumina with at least one purified stream selected from the group consisting of a stream of mineral acid(s) and a stream of alkylene(s).
3. The process as claimed in claims 1 and 2, wherein said mineral acid is at least one corrosive acid selected from the group consisting of hydrochloric acid, hydrofluoric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid and perchloric acid.

4. The process as claimed in claim 1, wherein said fluid stream is a hydrochloric acid stream.
5. The process as claimed in claims 1 and 2, wherein said alkylene is at least one selected from the group consisting of ethylene, methylene and propylene.
6. The process as claimed in claim 1, wherein said fluid stream is an ethylene stream.
7. The process as claimed in claim 1, wherein said metal contaminant is selected from the group consisting of iron, nickel, copper, chromium, lead, zinc, manganese and oxides thereof.
8. The process as claimed in claim 1, wherein said metal contaminant is iron oxide.
9. The process as claimed in claim 1, wherein said step of contacting is carried out at a temperature ranging between 20 °C and 200 °C.
10.The process as claimed in claim 1, wherein said step of contacting is carried out at a pressure ranging between 1 kg/ cm and 10 kg/ cm .
11.The process as claimed in claim 1, wherein said step of contacting is carried out at a gas hourly space velocity (GHSV) ranging between 10,000 per hour and 20,000 per hour.

12.The process as claimed in claim 1, wherein the shape of said macroporos alpha alumina is selected from the group of shapes consisting of bead shape and disc shape.