Process for utilizing reaction residues from manufacture of aqueous polymer dispersions

Abstract

The present invention concerns a process for utilizing at least one waste stream from a production plant for aqueous polymer dispersions from at least one type of monomer M, in which reaction residues are separated from water. Said reaction residues are optionally converted into a pyrolysis oil by a pyrolysis process, which pyrolysis oil is then converted by a gasification process into synthesis gas or said separated reaction residues as such are converted into synthesis gas by a gasification process. The synthesis gas may be used for synthesis of monomers M. The present invention further concerns a production plant for aqueous polymer dispersions comprising an integrated reaction residue treatment facility which is suited for said process.

Description

[0001] 240644W001

[0002] 1

[0003] Process for utilizing reaction residues from manufacture of aqueous polymer dispersions

[0004] Technical area

[0005] The present invention relates to a process utilizing reaction residues from manufacture of aqueous polymer dispersions, a plant for manufacture of aqueous polymer dispersions further comprising an integrated reaction residues treatment facility and the use of said plant for said process.

[0006] Background of the invention

[0007] Aqueous polymer dispersions of polymerized ethylenically unsaturated monomers, also referred to as polymer latices, are fluid systems comprising dispersed polymer particles of a chain growth addition polymer in an aqueous dispersing medium. Depending on the polymer architecture of the dispersed polymer particles, the polymer dispersions can be used across a plethora of technical applications, including binders for paints, architectural as well as industrial coatings, binders for paper coatings, binders in adhesives, binders for fiber bonding, organic opacifiers, rubbers and impact modifiers for thermoplastics.

[0008] The production of polymer dispersions, solutions and suspensions from the corresponding monomer units usually takes place continuously or batchwise, depending on the type of monomers used, in closed reactors (hermetically separated from the environment) or open reactors (not hermetically separated from the environment). After the end of the reaction and after the system has, if appropriate, been let down to atmospheric pressure, with optional recycling of the monomers, the contents of the reactor, which are often still at temperatures above 20 °C, must be transferred from the reactor into a “vessel” such as a buffer, conditioning or storage container. The production of polymer dispersions, solutions and suspensions from the corresponding monomer units is also referred to as “aqueous radical emulsion polymerization”.

[0009] Fouling occurs in such reactors and vessels (the word “vessel” as used and meant throughout this invention is defined further below), both in batch-wise and continuous polymerization processes. Fouling relates to the creation of occlusions in the reactor and / or vessel which occur when polymer deposits are formed at the reactor walls and / or vessel walls. “Fouling” is the accumulation of unwanted material, in the following named “reaction residues”, on solid surfaces, in particular surfaces in a reactor for polymerization and vessel(s) downstream of said reactor. Fouling is a particular problem as it decreases the reactor performance. Particularly, polymerization process may not take place as intended. Even the reactor may be damaged or destroyed. Thus, the prevention of fouling reduces the effort of reactor maintenance and avoids severe damage to the reactor. These reaction residues lead to an increase of the pressure drop of the reactor, to a reduction of the effective reactor volume with time and / or a change of the heat transfer properties of the reactor and ultimately force a shut-down and cleaning of the reactor. Furthermore, such fouling can result in contaminating a product with impurities caused by reaction residues, e.g., from a previous production batch using different monomers. Vessel(s) downstream of the reactor is / are affected by such fouling due to reaction residues in a similar manner. 240644W001

[0010] 2

[0011] Therefore, reactors and vessels are periodically cleaned to reduce the negative impact of fouling by reaction residues. In case of water-based polymer dispersions, polymer solutions and polymer suspensions, reactors and vessel(s) are usually cleaned by treating said reactors and vessel(s) with water. Thereby, reaction residues are removed from reactors and vessel(s). The water used for cleaning takes up said reaction residues and thereby an aqueous waste stream is formed.

[0012] A standard method for treatment of the aqueous waste streams (“reaction residues”) from production of waterbased (“aqueous”) polymer dispersions is incineration of said waste streams for example in a boiler in which steam can be produced. Thereby, undesired CO2 is formed. Another method for treatment of said waste streams is biological wastewater treatment such as anaerobic fermentation which produces methane and sludge. Said sludge is then treated by aerobic fermentation which produces undesired CO2.

[0013] EP4219412A1 discloses a process for treating industrial wastewater containing fluoropolymer particles and molecular fluoroorganic compounds. Both pyrolysis and gasification of fluoropolymer particles or molecular fluoroorganic compounds result in formation of hydrogen fluoride (HF) as side product which is highly undesirable due to its toxicity and severe corrosion caused by HF at high temperatures employed during pyrolysis and gasification.

[0014] WO2026 / 162290A1 discloses a method of purifying wastewater generated during an aqueous emulsion polymerization process for acrylonitrile butadiene styrene resins (ABS resins). Hence, said wastewater results from water utilized during synthesis of said ABS resin and not from cleaning the reactor with water after the ABS resin and the aqueous phase were purged from said reactor. The desired reaction product ABS resin is separated from the aqueous phase and said aqueous phase (wastewater) is then treated by a biological treatment process such as fermentation during which sludge is formed. Precipitates separated from wastewater before said biological treatment process have a high content of inorganics. Further targets of the process are a) to make organics treatable in biotreatment and b) to make wastewater after said treatment reuseable.

[0015] EP0921182A1 discloses a method for processing waste or biomass into valuable products such as combustible gases. Waste or biomass is first subjected to a pyrolysis, the resulting gaseous pyrolysis products (“without condensation”, i.e., without separating a pyrolysis oil therefrom) are directly subjected to a thermal cracking process “under the influence of oxygen-rich gas”, and the solid residues from the pyrolysis are subjected to a gasification process. Accordingly, said document does not disclose gasification of a waste or biomass derived pyrolysis oil.

[0016] It is an objective of the present invention to utilize the reaction residues from production of aqueous polymer dispersions described above in a more sustainable way than incineration. 240644W001

[0017] 3

[0018] It is a further objective of the present invention to provide a process and a production plant which convert at least a portion of said reaction residues into feedstocks for the chemical industry.

[0019] It is a further objective of the present invention, to provide a process for converting said reaction residues into monomers M from which aqueous polymer dispersions can be manufactured.

[0020] Summary of the invention

[0021] These problems are solved by a process for utilizing at least one waste stream from a production plant for aqueous polymer dispersions from at least one type of monomer M, wherein said production plant comprises a) at least one reactor R,

[0022] b) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R, and

[0023] c) a means MC for collecting reaction residue loaded water RRLW,

[0024] and wherein the process comprises the steps

[0025] (i) providing at least one type of monomer M, wherein said at least one type of monomer M is an ethylenically unsaturated monomer selected from the group consisting of monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylate esters, methacrylate esters, acrylic acid, methacrylic acid, amides of acrylic acid, amides of methacrylic acid, acrylonitrile, vinyl esters of C2-Ci2-alkanoic acids, allyl esters of C2-Ci2-alkanoic acids and mixtures thereof,

[0026] (ii) producing by a polymerization reaction from said at least one type of monomer M at least one reaction product RP in said at least one reactor R whereby also reaction residues RR are formed,

[0027] (iii) optionally transferring said at least one reaction product RP and at least a portion of said reaction residues RR from said at least one reactor R into said at least one vessel V,

[0028] (iv) removing said at least one reaction product RP from said at least one reactor R and / or said at least one optional vessel V,

[0029] (v) providing water W to said at least one reactor R and / or said at least one optional vessel V and cleaning said at least one reactor R and / or said at least one optional vessel V with said water W,

[0030] (vi) removing at least a portion of said reaction residues RR from said at least one reactor R and / or said at least one vessel V with said water W whereby reaction residue loaded water RRLW is formed,

[0031] (vii) separating said reaction residue RR from said reaction residue loaded water RRLW and thereby forming a separated reaction residue SRR, and optionally drying said separated reaction residue SRR and thereby forming a dried separated reaction residue DSRR,

[0032] (viii) optionally subjecting said separated reaction residue SRR and / or said dried separated reaction residue DSRR to a pyrolysis reaction and thereby forming a pyrolysis oil PO,

[0033] (ix) subjecting at least one member selected from the group consisting of separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO and combinations thereof to a partial oxidation reaction in at least one gasifier G and thereby forming a gas stream GS1, said gas stream GS1 comprising CO, H2 and CO2 and 240644W001

[0034] 4

[0035] (x) cleaning said gas stream GS1 and thereby forming a gas stream GS2.

[0036] These problems are further solved by a production plant for aqueous polymer dispersions comprising an integrated reaction residue treatment facility wherein said production plant comprises

[0037] (i) at least one reactor R,

[0038] (ii) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R,

[0039] (iii) a means MO for collecting reaction residue loaded water RRLW, said means MO downstream of and fluidically connected to said at least one reactor R and / or said at least one vessel V,

[0040] (iv) at least one further means MS for separating the reaction residue RR from said reaction residue loaded water RRLW and optionally for drying the reaction residue RR separated from said reaction residue loaded water RRLW and

[0041] (v) at least one gasifier G, said at least one gasifier G downstream of and directly or indirectly fluidically connected to said means MS

[0042] or at least one pyrolysis reactor PR, said at least one pyrolysis reactor PR downstream of and directly or indirectly fluidically connected to said means MS.

[0043] The process and production plant according to the present invention enable a utilization of the reaction residues from production of aqueous polymer dispersions in which said reaction residues are converted into synthesis gas which is an important feedstock for the (petro-)chemical industry. Optionally, pyrolysis oil formed by pyrolysis of said reaction residues may also be used as a feedstock for a cracking process such as a steam cracking process. Furthermore, the amount of undesired CO2 as a co-product of the treatment of said reaction residues is reduced in comparison to state-of-the-art treatment methods for such reaction residues. In addition, the synthesis gas produced from the process and production plant according to the present invention can be converted (depending on the process path together with further feedstocks) into ethylenically unsaturated monomers M which then serve as a or the feedstock to produce aqueous polymer dispersions. The process and production plant according to the present invention are suited for a closed-loop recycling of the main waste stream formed during production of aqueous polymer dispersions.

[0044] Detailed description of the invention

[0045] The present invention is further described below with reference to the embodiments, but the present invention is not limited to these embodiments, and any modifications of these embodiments, combinations of these embodiments or substitutions within the basic spirit of the present invention are still within the scope of the present invention as claimed.

[0046] Definitions:

[0047] In the context of the present description and the accompanying claims, the term “about’ preferably means a deviation of the thus described value of ±10 %. In the context of the present invention, the term “combinations 240644W001

[0048] 5

[0049] thereof” is inclusive of one or more of the recited elements. In the context of the present invention, the term “mixture thereof” is inclusive of one or more of the recited elements.

[0050] The term “at least one” includes one or two or three or four or five or six or a higher number. For example, “at least one type of monomer M” may include one monomer M1 or two different monomers M1 or one monomer M1 and one monomer M2 or two different monomers M1 and one monomer M2 or one monomer M1 and one monomer M2 and one monomer M3 and so on.

[0051] “ppmw” is defined herein as a parts-per-million notation referring to a mass fraction.

[0052] By “vessel V” are meant buffer vessels, conditioning vessels, storage containers, transportation containers, drums, canisters and cans, etc. of a very wide variety of sizes and forms. The material from which the vessels are constructed is unimportant in this context. These “vessel V” may comprise a wide variety of different internals, examples being stirrers, heat exchangers, heating and / or cooling coils, flow disruptors and sensors, externals such as heat exchangers and condensers, and a wide variety of connections and openings, which may also be closable by way of closures, such as ballcocks, valves of various construction, and screw covers, etc.

[0053] The term “downstream of” is defined herein in respect to a succession of unit operations as located next to on the side (or above, below) which is in the flow direction of fluids passing said succession of unit operations.

[0054] The term “fluidically connected to” in respect to two or more units is defined herein that a fluid such as a particulate solid, liquids, gases, and mixtures thereof can flow from one of such unit to the other such unit. Two units “fluidically connected to” each other are for example connected by one or more pipes which each other or by screw conveyors or by extruders or by solids pumps.

[0055] “Refuse-derived fuel” (RDF) is defined herein as a fuel produced from various types of waste such as municipal solid waste (MSW), industrial waste or commercial waste. RDF consists largely of combustible components of such waste, as non-recyclable plastics (preferably not including PVC), paper cardboard, labels, and other corrugated materials. These fractions are separated by different processing steps, such as screening, air classification, ballistic separation, separation of ferrous and non-ferrous materials, glass, stones, and other foreign materials and shredding into a uniform grain size, or also pelletized to produce a homogeneous material which can be used as a feedstock for gasification processes (Y. Yang et al., Gasification of refuse-derived fuel from municipal solid waste for energy production: a review, Environmental Chemistry Letters (2021) 19, 2127-2140 (https: / / doi.Org / 10.1007 / s 10311 -020-01177-5).

[0056] The process for utilizing reaction residues from a production plant for aqueous polymer dispersions according to the present invention is described below in detail. 240644W001

[0057] 6

[0058] At least one monomer M is provided in step (i) of the process according to the present invention. Said at least one type of monomer M is an ethylenically unsaturated monomer selected from the group consisting of monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylate esters, methacrylate esters, acrylic acid, methacrylic acid, amides of acrylic acid, amides of methacrylic acid, acrylonitrile, vinyl esters of C2-Ci2-alkanoic acids, allyl esters of C2-Ci2-alkanoic acids and mixtures thereof. Preferably, said at least one type of monomer M is a monomer M1 or in case of two or more types of monomer M provided in step (i) and polymerized in step (ii), said two or more types of monomer M comprise at least one monomer M1.

[0059] Preferably, the monomers M are to be polymerized in a radical aqueous emulsion polymerization and typically comprise at least 80 wt.-%, e.g. 80 to 100 wt.-%, or 80 to 99.9 wt.-%, in particular 85 to 99.9 wt.-%, based on the total weight of the preferred monomers M, of one or more ethylenically unsaturated monomers M, which have a limited solubility in water, in particular a solubility in deionized water, which does not exceed 50 g / L at 20 °C and 1 bar(abs.). These monomers are hereinafter referred to as monomers M1. The solvent used during the radical emulsion polymerization is most preferably water.

[0060] Examples of such monomers M1 include in particular

[0061] acrylate esters and methacrylate esters, in particular esters of acrylic and esters of methacrylic acid with alkanols having 1 to 18 C atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylpentyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, Cw isoamyl guerbet acrylate, 1 -propylheptyl acrylate, lauryl acrylate and stearyl acrylate. Examples of C1-C20 alkyl esters of methacrylic acid include, but are not limited to methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2- butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylpentyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, Cw isoamyl guerbet methacrylate, 1 -propylheptyl methacrylate, lauryl methacrylate and stearyl methacrylate;

[0062] esters of acrylic and / or methacrylic acid with cycloalkanols having 3 to 18 C atoms, in particular 5 to 10 C atoms, such as cyclopropylacrylate, cyclopentyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate and 4-tert-butylcyclohexyl methacrylate;

[0063] monovinylaromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4- n-butylstyrene or 4-n-decylstyrene;

[0064] conjugated alkadienes, such as butadiene or isoprene;

[0065] olefins and haloolefins such as ethylene, propene, vinyl chloride, and vinylidene chloride, preferably not fluoroolefins; 240644W001

[0066] 7

[0067] vinyl esters and allyl esters of saturated C1-C12 alkanoic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl stearate, vinyl esters of Versatic acid, allyl formate, allyl acetate, allyl propionate, allyl butyrate or allyl laurate.

[0068] More preferred monomers M1 are esters of acrylic acid with alkanols having 1 to 10 C atoms, esters of methacrylic acid with alkanols having 1 to 10 C atoms, monovinylaromatic hydrocarbon compounds, specifically styrene, conjugated alkadienes, specifically butadiene, vinyl esters of saturated C1-C12 alkanoic acids, specifically vinylacetate, vinyl propionate and vinyl versatate, and olefins, specifically ethylene and combinations thereof.

[0069] In particular, the monomers M1 are one of the following monomer combinations (1) to (5):

[0070] (1) at least one monovinyl aromatic monomer, at least one acrylate ester and optionally one or more methacrylate esters,

[0071] (2) at least one acrylate ester and at least one methacrylate ester,

[0072] (3) at least one monovinyl aromatic monomer, butadiene and optionally one or more monomers selected from acrylate esters and methacrylate esters

[0073] (4) at least one vinylester of a C2-Ci2-alkanoic acid;

[0074] (5) at least one vinylester of a C2-Ci2-alkanoic acid and at least one C2-C4-monoolefine and optionally one of acrylate esters and methacrylate esters.

[0075] Besides the monomers M1, the monomers to be polymerized in the aqueous radical emulsion polymerization may comprise one or more ethylenically unsaturated monomers which are different from the monomers M1 , which are in particular selected from the monomers M2, M3 and M4 described hereinafter. The total amount of these monomers is typically in the range of 0 to 20 wt.-%, e.g., in the range of 0.1 to 20 wt.-%, based on the total weight of the monomers M. In such cases, the monomer M can also be considered a monomer composition M, said monomer composition comprising monomers M1 and M2, or M1, M2, M3, or M1, M2, .... Mn, wherein n is an integer.

[0076] Examples for monomers M2 are monoethylenically unsaturated acidic monomers M2.a such as monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms such as acrylic acid, methacrylic acid or itaconic acid;

[0077] ethylenically unsaturated sulfonic acids and their salts such as vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3- acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acids, and 2-acrylamido-2-methylpropanesulfonic acid, especially their salts, more particularly their sodium salts and their ammonium salts;

[0078] ethylenically unsaturated phosphonic acid and ethylenically unsaturated phosphoric acids and their salts such as vinylphosphonic acid, allylphosphonic acid, phosphoethyl acrylate, phosphoethyl methacrylate, phosphopropyl acrylate, phosphopropyl methacrylate, phospho-oligo(C2-C3-alkyleneether)acrylate, 240644W001

[0079] 8

[0080] phospho-ol i go(C2-C3-al kyleneetheijmethacry I ate, especially their salts, more particularly their sodium salts and their ammonium salts;

[0081] and monoethylenically unsaturated neutral monomers M2.b, such as

[0082] primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms such as acrylamide and methacrylamide;

[0083] monoethylenically unsaturated monomers which carry urea groups or keto groups, such as 2-(2- oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, N-[2-(2-oxo-oxazolidin-3-yl)ethyl] methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM) and diacetonemethacrylamide;

[0084] esters of acrylic and / or methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2- hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate;

[0085] Preferably, the monomers M contain not more than 5 pphm (“parts per hundred million”), e.g. 0.1 to 5 pphm of monoethylenically unsaturated monomers M2.a having an acid group. Preferably, the monomers M contain not more than 10 pphm of monomers M2.b, e.g., 0 to 10 pphm or 0.1 to 10 pphm of monomers M2.b.

[0086] In addition to the aformementioned monoethylenically unsaturated monomers monomers M1 and M2, the monomers M may comprise a small amount of ethylenically unsaturated monomers M3, which bear at least 2, e.g. 2 to 6 non-conjugated ethylenically unsaturated double bonds. These monomers will result in a crosslinking of the polymer chain during polymerization and thus are referred to as crosslinking monomers M3. Exemplary crosslinking monomers include divinylbenzene, diesters or triesters of dihydric and trihydric alcohols with monoethylenically unsaturated Ca-Ce monocarboxylic acids, e.g., di(meth)acrylates, tri(meth)acrylates), and tetra(meth)acrylates, e.g. alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1 ,3-butylene glycol diacrylate, 1 ,4-butylene glycol diacrylate and propylene glycol diacrylate, trimethylolpropan triacrylate and trimethacrylate, pentaerythrit triacrylate and pentaerythrit tetraacrylate, but also vinyl and allyl esters of ethylenically unsaturated acids such as vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, and divinyl and diallyl esters of dicarboxyilic acids, such as diallyl maleate and diallyl fumarate and also methylenebisacrylamide. The amount of said monomers M3 will usually not exceed 3 pphm and, if present, is in particular in the range of 0.01 to 3 pphm.

[0087] In addition to the aforementioned monoethylenically unsaturated monomers monomers M1 and M2, the monomers M may comprise a small amount of ethylenically unsaturated monomers M4, which have one unsaturated double bond and a further reactive group susceptible to a post-crosslinking reaction, including monoethylenically unsaturated monomers containing a keto group, e.g., acetoacetoxyethyl(meth)acrylate or diacetonacrylamide; 240644W001

[0088] 9

[0089] monoethylenically unsaturated monomers, which bear an epoxy group, such as monoeglycidyl allyl ether, glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 3- glycidyloxypropyl acrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl acrylate 4-glycidyloxybutyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5-epoxypent-2-yl acrylate or 4,5- epoxypent-2-yl methacrylate with preference given to epoxy functionalized (meth)acrylate monomers; N-alkylolamides of a,|3-monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms and esters thereof with alcohols having 1 to 4 carbon atoms, e.g. N-methylol acrylamide and N-methylol methacrylamide;

[0090] unsaturated silan functional monomers, e.g. monomers which in addition to an ethylenically unsaturated double bond bear at least one mono-, di- and / or tri-Ci -C^al koxysilane group, such as vinyl trimethoxysilane, vinyl triethoxysilane, methacryloxyethyl trimethoxysilane, methacryloxyethyl triethoxysilane, and mixtures thereof.

[0091] The amount of said monomers M4 will usually not exceed 10 pphm and is in particular in the range of 0.01 to 10 pphm.

[0092] Next, at least one reaction product RP is produced by a polymerization reaction, preferably a radical aqueous emulsion polymerization, from said at least one type of monomer M provided in step (i) in at least one reactor R. The at least one reaction product RP is selected from the group comprising or preferably consisting of polymer dispersions, polymer solutions and polymer suspensions which are all referred to as “polymer dispersions” in respect to the present invention. Preferably, said at least one reaction product RP is not a fluoropolymer. Preferably, no fluoroorganic compounds are provided in step (i) and / or present in the polymerization reaction of step (ii).

[0093] The production of polymer dispersions, polymer solutions and polymer suspensions (reaction product RP) from the corresponding monomer M usually takes place continuously or batchwise in at least one reactor R.

[0094] Depending on the monomer units used for the polymerization and the liquid medium used to take up the polymers, the reaction often takes place under an inert gas atmosphere (preferably in a closed reactor), at elevated temperature, and, if desired, under superatmospheric pressure. Monomers which do not require an inert gas atmosphere during step (ii) may also be polymerized in an open reactor which is open to the environment, e.g., to air. After the end of the reaction and after the system has, if appropriate, been let down to atmospheric pressure, with recycling of the monomers, the contents of the at least one reactor R, which are often still at temperatures above 20 °C, must be transferred from the at least one reactor R into a the at least one vessel V, which at least one vessel V is downstream of and fluidically connected to said at least one reactor R. The at least one vessel V can be for example a buffer vessel, a conditioning vessel and / or a storage container.

[0095] The general production and processing of polymer dispersions [cf. e.g., Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659ff. (1987); D. C. Blackley, in High Polymer Latices, Vol. 1, p. 35ff. (1966); Emulsion 240644W001

[0096] 10

[0097] Polymerisation, Interscience Publishers, Inc. (1965), and Dispersionen synthetischer Hochpolymerer, F.

[0098] Hblscher, Springer Verlag (1969) and also Ullmanns Encyclopadie der technischen Chemie, 4th ed., Vol. 19, p.

[0099] 132ff.], polymer suspensions [cf. e.g. Encyclopedia of Polymer Science and Engineering, Vol. 16, p. 443ff. (1989); High Polymers, Vol. X, Polymer Processes, Interscience Publishers, Inc., p. 69ff. (1956); High Polymers, Vol. XXIX, Polymerization Processes, John Wiley & Sons, Inc., p. 106ff. (1977); Ullmanns Encyclopadie der technischen Chemie, 4. ed., Vol. 19, p. 125ff.] and polymer solutions [cf. e.g., Encyclopedia of Polymer Science and Engineering, Vol. 15, p. 402ff. (1989); High Polymers, Vol. X, Polymer Processes, Interscience Publishers, Inc., p. 175ff. (1956); High Polymers, Vol. XXIX, Polymerization Processes, John Wiley & Sons, Inc., p. 198ff. (1977); Ullmanns Encyclopadie der technischen Chemie, 4th ed., Vol. 19, p. 112ff.] have been described on many occasions in the past and are therefore sufficiently well known to the skilled worker.

[0100] A particularly preferred type of polymer dispersions as reaction product RP in the process according to the present invention are aqueous polymer dispersions. Aqueous polymer dispersions are typically produced by aqueous emulsion polymerization, in particular prepared by a free radical aqueous emulsion polymerization of ethylenically unsaturated monomers, which include monovinyl aromatics such as styrene or vinyl toluene, mono-and diolefins, such as butadiene, isoprene or ethene, esters of a, B-ethylenically unsaturated acids, in particular the esters of acrylic acid or methacrylic acid, vinyl or allyl ethers and vinyl or allyl esters, and combinations thereof. The term “free radical aqueous emulsion polymerization” means that the polymerization of the monomers M is initiated by radicals formed by the decay of a polymerization initiator, whereby free radicals are formed in the polymerization mixture. It is therefore also termed “radically initiated emulsion polymerization”. The procedure for radically initiated emulsion polymerizations of monomers in an aqueous medium has been extensively described and is therefore sufficiently familiar to the skilled person [cf. in this regard Emulsion Polymerization in Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 ff. (1987); D.C. Blackley, in High Polymer Latices, vol. 1, pages 35 ff. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, chapters, pages 246 ff. (1972); D. Diederich, Chemie in unserer Zeit 24, pages 135 to 142 (1990); Emulsion Polymerisation, Interscience Publishers, New York (1965); DE-A 4003422; and Dispersionen synthetischer Hochpolymerer, F. Hblscher, Springer-Verlag, Berlin (1969), D. Urban, K. Takamura (ed.) ..Polymer Dispersions and Their Industrial Applications", Wiley VCH, Weinheim 2002)]. Detailed mechanistic studies have been summarized e. g. by C. S. Chern, Prog. Polym. Sci. 31 (2006) 443-486; and by M. Nomura et al., Adv. Polym. Sci. 175 (2005) 1-128.

[0101] The aqueous reaction medium in polymerization may in principle also comprise minor amounts (usually at most 5 wt.-%) of water-soluble organic solvents, for example methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc. Preferably, however, the process of the invention is conducted in the absence of such solvents.

[0102] The radical aqueous emulsion polymerization may be carried out by a single stage or by a multistage emulsion polymerization, in particular an aqueous radical emulsion polymerization, of a monomer composition M comprising at least one type of monomer M. The term "multistage" in the context of aqueous emulsion polymerization is well understood to mean that the relative concentration of the monomers in the monomer 240644W001

[0103] 11

[0104] composition M added to the polymerization reaction is altered at least once during the aqueous emulsion polymerization. Such a procedure results in at least two polymer populations of different monomer compositions in the polymer particles of the latex. For example, it will be possible to change the monomer composition such that the multistage latex polymer features populations having different glass transition temperatures or a glass transition temperature (Tg) gradient.

[0105] The concentration of the polymer contained in the aqueous polymer dispersion is frequently in the range from 20 to 70 wt.-%, in particular in the range from 30 to 65 wt.-%, especially in the range from 40 to 65 wt.-%, based in on the total weight of the aqueous polymer dispersion.

[0106] In suitable aqueous polymer dispersion, the dispersed polymers are in the form of polymer particles. The polymer particles typically have an average diameter in the range from 30 to 1000 nm, in particular in the range from 40 to 900 nm and especially in the range from 50 to 800 nm. The average particle diameter as referred herein relates to the Z average particle diameter as determined by means of photon correlation spectroscopy (PCS), also known as quasielastic light scattering (QELS) or dynamic light scattering (DLS). The measurement method is described in the ISO 13321:1996 standard.

[0107] Optionally, said at least one reaction product RP is transferred in step (iii) from the at least one reactor R to at least one vessel V, which at least one vessel V is downstream of and fluidically connected to said at least one reactor R. The at least one vessel V is selected from the group comprising buffer vessels, conditioning vessels, storage containers, transportation containers, drums, canisters and cans.

[0108] The reaction product RP is subjected to a workup in said at least one vessel V. Said workup may comprise chemical and / or physical reduction of residual monomers VOC, conditioning of the reaction product RP (e.g., adjustment of the solid content, addition of at least one biocide, control and adjustment of the pH value of the reaction product), filtration of the reaction product RP and combinations thereof.

[0109] Next, the at least one reaction product RP is removed from said at least one reactor R and / or said at least one optional vessel V. At least a portion of said reaction residues RR also formed in step (ii) remain in the at least one reactor R and / or the optional at least one vessel V. Accordingly, said reaction residues RR are accumulated during each batch of reaction product RP formed in said at least one reactor R or, in case of a continuous polymerization, over time of continuous production. Said reaction residues RR form for examples deposits on the inner wall and other internals of the at least one reactor R and the optional at least one vessel V.

[0110] Water W is provided to said at least one reactor R and / or said at least one optional vessel V and cleaning said at least one reactor R and / or said at least one optional vessel V with said water W in step (v). The water W can be cold water, water having an ambient temperature or hot water. Preferably water W has a temperature in the range 1 to 200 °C, more preferably 2 to 180 °C and most preferably 5 to 150 °C. Water W having a temperature in said 240644W001

[0111] 12

[0112] ranges is even more suited to remove the reaction residues RR from the at least one reactor R and the optional at least one vessel V in step (vi). Optionally, the pH value of said water W is adjusted in the range of 6 to 9 and / or one or more solvents is / are added to said water W and / or one or more surfactant is added to said water W. Suitable pH values and optional solvents and / or surfactants can be selected and applied by the skilled person.

[0113] Thereby, reaction residue loaded water RRLW is formed. The reaction residue loaded water RRLW preferably comprises less than 4 wt.-%, more preferably 0.1 to 3 wt.-%, and most preferably 0.5 to 2 wt.-% reaction residue RR.

[0114] Accordingly, the reaction residue loaded water RRLW is derived from cleaning said at least one reactor R and / or said at least one optional vessel V after the reaction products and the water present during polymerization were removed from said at least one reactor R and / or said at least one optional vessel V. The reaction residue loaded water RRLW comprises said reaction residue RR. In contrast, water purged together with the reaction products after the polymerization reaction from at least one reactor R and / or at least one vessel V comprises said reaction products (e.g., a polymer dispersion). Hence, in the latter case no reaction residue loaded water RRLW comprising said reaction residue RR is purged from at least one reactor R and / or at least one vessel V.

[0115] Water W can be contacted with the reaction residue RR in various ways. Parameters such as water W temperature, water W pressure and the retention time of water W in the at least one reactor R and optional vessel(s) V can be adopted by the skilled person for a given type of reaction residue RR, reactor design and the like. Accordingly, the means and methods for removing the reaction residue RR provided herein are mere examples. Other, not specifically disclosed means and methods can be chosen by the skilled person.

[0116] The reaction residue RR can be removed with water W by using a simple hose, optionally equipped with a nozzle and / or a pump, for increasing and / or decreasing the water W pressure, and / or providing a desired shape of the water W stream. Reaction residues RR can also be removed by using spray jets or an array of spray jets, which spray jets or array of spray jets moves upwards and / or downwards or with any other type of movement such as an oscillation movement along the inner surface of the at least one reactor R and the optional at least one vessel V. Said movement of spray jets or array of spray jets can be a manual and / or automated movement. One type of spray jets suited for step (vi) is for example described in Encyclopedia of Polymer Science and Engineering, Vol.

[0117] 12, p. 536 (1988): spray jets are permanently installed in the reactor head and from which, during step (vi) water is sprayed in as a cleaning fluid. Another type of spray jets suited for step (vi) comprise spray jets not permanently installed but only temporary installed for cleaning. Also suited are high pressure cleaning devices like lance or tank washing head, preferably with a water pressure of 100 to 300 bar, more preferably 400 to 2000 bar.

[0118] The reaction residue RR is usually not chemically dissolved in water W but rather dispersed therein. Accordingly, step (vi) is rather a mechanical cleaning process than a chemical process. Preferably, the residue loaded water 240644W001

[0119] 13

[0120] RRLW is not subjected to a biological treatment process such as fermentation before said reaction residue RR is separated from said reaction residue loaded water RRLW.

[0121] Next, said reaction residue RR is separated in step (vii) from said reaction residue loaded water RRLW. This step is required because the reaction residue loaded water RRLW only comprises preferably less than 4 wt.-%, more preferably 0.1 to 3 wt.-%, and most preferably 0.5 to 2 wt.-% reaction residue RR. The amount of production waste is reduced because only said separated reaction residue SRR needs further treatment while the water W can be reused, preferably for the next cycle of the process according to the present invention or used otherwise, e.g., after further treatment. In case of polymer dispersions, separating said reaction residue RR is difficult because of the small particle size of said reaction residue RR.

[0122] Separation of the reaction residue RR from said reaction residue loaded water RRLW can be archived by various methods which are known to the skilled person and can be adapted accordingly. Suitable methods comprise coagulation, flocculation, precipitation and combinations thereof.

[0123] Preferably, the reaction residue RR is separated from said reaction residue loaded water RRLW by at least one of the following steps: adding at least one type 1 additive to said reaction residue loaded water RRLW, adding at least one type 2 additive to said reaction residue loaded water RRLW, changing the pH value of said reaction residue loaded water RRLW, mechanical shearing of said reaction residue loaded water RRLW, electrical coagulation of said reaction residue loaded water RRLW, and combinations thereof. Combinations can be of any order, e.g., first adding a type 1 additive, then changing the pH value of the reaction residue loaded water RRLW, or first changing the pH value of the reaction residue loaded water RRLW and then adding a type 1 additive, and so on.

[0124] More preferably, the reaction residue RR is separated from said reaction residue loaded water RRLW by - adding at least one type 1 additive or

[0125] - adding at least one type 2 additive or

[0126] - changing the pH value of the reaction residue loaded water RRLW or

[0127] - adding at least one type 1 additive and at least one type 2 additive or

[0128] - adding at least one type 1 additive and changing the pH value of the reaction residue loaded water RRLW or - adding at least one type 1 additive and changing the pH value of the reaction residue loaded water RRLW and adding at least one type 2 additive or

[0129] - changing the pH value of the reaction residue loaded water RRLW and adding at least one type 1 additive or - changing the pH value of the reaction residue loaded water RRLW and adding at least one type 2 additive or - adding at least one type 1 additive and at least one type 2 additive and changing the pH value of the reaction residue loaded water RRLW or

[0130] - adding at least one type 1 additive and changing the pH value of the reaction residue loaded water RRLW and adding at least one type 2 additive and changing the pH value of the reaction residue loaded water RRLW. 240644W001

[0131] 14

[0132] The at least one type 1 additive is selected from the group comprising or preferably consisting of metal salts. The at least one type 1 additive is preferably an acidic metal salt which is water soluble. More preferably the at least one type 1 additive is selected from the group comprising or preferably consisting of aluminum sulfate, ferric chloride, aluminium chloride, polyaluminium chloride PAG, ferric sulfate and combinations thereof. The at least one type 1 additive (or the sum of all type 1 additives in case more than one type 1 additive is added to said reaction residue loaded water RRLW preferably ranges from 0.03 to 100 g / l, more preferably 0.1 to 10 g / l.| The at least one type 1 additive is preferably dissolved or diluted in water before added to said reaction residue loaded water RRLW.

[0133] The at least one type 2 additive is selected from the group comprising or preferably consisting of anionic polymers, cationic polymers and combinations thereof. Preferably, the at least one type 2 additive is a homo- or copolymer, either linear or branched, comprising at least one building unit selected from the group comprising or preferably consisting of acrylamide, acrylic acid, dimethylamine, methacrylamide, N-vinylformamide, vinylamine, methacrylic acid, acrylonitrile, vinyl acetate. More preferably, the at least one type 2 additive is selected from the group comprising or preferably consisting of polyacrylamide, polyvinylamine, polyethylenimine and combinations thereof. The at least one type 2 additive (or the sum of all type 2 additives in case more than one type 2 additive is added to said reaction residue loaded water RRLW preferably ranges from 0.03 to 100 g / l, more preferably 0.1 to 10 g / l. The at least one type 2 additive is preferably dissolved or diluted in water before added to said reaction residue loaded water RRLW.

[0134] The pH value of the reaction residue loaded water RRLW is preferably changed by adding at least one inorganic substance having an acidic or alkaline pH value thereto. More preferably, the at least one inorganic substance having an alkaline pH value is selected from the group comprising or preferably consisting of sodium hydroxide, potassium hydroxide, calcium carbonate, calcium hydroxide, and combinations thereof. More preferably, the at least one inorganic substance having an acidic pH value is selected from the group comprising or preferably consisting of hydrochloric acid, sulfuric acid and combinations thereof. The pH value of the reaction residue loaded water RRLW has preferably a pH value in the range of 4 to 8 after addition of the at least one inorganic substance having an acidic or alkaline pH value. The pH value of the reaction residue loaded water RRLW can be measured for example with standard pH electrodes because it is an aqueous system.

[0135] Suitable type 1 additives and / or type 2 additives, pH values and optional further process steps for reaction residue loaded water RRLW depend on various factors, such as the chemical composition of the reaction residue RR, the desired particle size, and the stability of the dispersion. The choice of type 1 additive(s) and / or type 2 additive(S) and conditions applied in step (vii) can be optimized for each specific aqueous polymer dispersion by the skilled person to achieve the desired particle size and stability. 240644W001

[0136] 15

[0137] Next, the precipitated reaction residue RR can then be separated from water W in the reaction residue loaded water RRLW for example by gravity (e.g., by settling), decantation, filtration (e.g., in a filter press), centrifugation, in a screw press and combinations thereof which results in the separated reaction residue SRR. One or more filter aid(s), preferably based on cellulose may be added to improve separation of the precipitated reaction residue RR from water.

[0138] The separated reaction residue SRR obtained by the procedure described above usually still comprises 40 to 60 wt.-% water W. Accordingly, the separated reaction residue SRR is suited for further treatment in optional step (viii) and step (ix).

[0139] Preferably, the water content of the separated reaction residue SRR is further reduced whereby a dried separated reaction residue DSRR is formed. Said dried separated reaction residue DSRR is even more suited for further treatment in optional step (viii) and step (ix) than the separated reaction residue SRR because less water needs to be co-treated in optional step (viii) and step (ix).

[0140] The separated reaction residue SRR is preferably dried with a hot gas such as hot air. More preferably, the separated reaction residue SRR is dried with at least means selected from the group comprising or consisting of belt dryer, oven cabinet, screw dryer, paddle dryer, fluidized bed dryer, kneader and combinations thereof. Predrying with e.g., hot gas may be applied directly after separation of the precipitated reaction residue RR from water W in, for example, a filter press.

[0141] Hot gas such as hot air is preferably obtained as waste heat from one or more other process(es).

[0142] The dried separated reaction residue DSRR preferably comprises 10 to 20 wt.-% water W, more preferably no more than 10 wt.-% water W and most preferably no more than 7.5 wt.-% water W.

[0143] Preferably, said reaction residue RR has at least one, more preferably all the following properties:

[0144] a) a carbon content in the range of 50 to 90 wt.-%, more preferably 70 to 90 wt.-% and most preferably 80 to 90 wt.-%,

[0145] b) a hydrogen content in the range of 5 to 15 wt.-%, more preferably 7 to 10 wt.-% and most preferably c to d wt.-%,

[0146] c) an oxygen content in the range of 0 to 40 wt.-%, more preferably 0 to 20 wt.-% and most preferably 0 to 10 wt.-%, and

[0147] d) a nitrogen content in the range of 0 to 20 wt.-%, more preferably 0 to 10 wt.-% and most preferably 0 to 2 wt.-%.

[0148] The dried separated reaction residue DSRR preferably has a calorific value in the range of 20 to 45 M J / kg, more preferably of 30 to 40 M J / kg and most preferably of 35 to 40 M J / kg. 240644W001

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[0150] Analytical methods suitable for measuring the calorific value of a feedstock such as the dried separated reaction residue DSRR comprise combustion of a sample of said feedstock in a bomb calorimeter. Such methods are for example suitable to assess the thermochemical behavior of said feedstock during the gasification reaction and, accordingly, the suitable type of gasifier and gasification process parameters such as temperature, amount, and type of oxidant.

[0151] Analytical methods suitable for measuring the elemental composition such as the content of chemical elements H, C, 0, N, and S of a feedstock such as the reaction residues RR comprise CH NX analysis by combustion combined with thermal conductivity detection and / or infrared spectroscopy.

[0152] Next, the separated reaction residue SRR and / or the dried separated reaction residue DSRR are subjected to a pyrolysis reaction in a pyrolysis reactor PR in optional step (viii) whereby a pyrolysis oil PO is formed. Most preferably, the dried separated reaction residue DSRR is subjected to a to a pyrolysis reaction in a pyrolysis reactor PR in optional step (viii).

[0153] The separated reaction residue SRR and / or the dried separated reaction residue DSRR is inserted into a pyrolysis reactor PR using a dosing unit such as for example a screw or an extruder or a rotary valve or a pneumatic conveyor or a liquid injector. Next, the separated reaction residue SRR and / or the dried separated reaction residue DSRR is heated in the pyrolysis reactor PR. The temperature in said pyrolysis reactor PR preferably ranges from 400 to about 600 °C. The pressure in the pyrolysis reactor PR ranges from about 0.5 to about 2 bar(abs), more preferably in the range of from 0.9 bar to about 1.5 bar(abs). Pyrolysis processes as such are known. They are described, e.g., in EP 0713906 A1, WO 95 / 03375 A1 and Jorg Woidasky, Ullmanns Encyclopedia of Industrial Chemistry, chapter 5.2.1 “Pyrolysis”, pages 15-17, 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim (DOI: 10.1002 / 14356007.a21_057.pub2).

[0154] The pyrolysis reactor PR is preferably selected from the group comprising fluidized bed reactors, moving bed reactors, entrained flow reactors, stirred tank reactors, rotary kiln reactors and reactors comprising a reactor chamber and a rotation mechanism. Said rotation mechanism can be for example conveyor screws, conveyor double screws, kneaders, hammer mills, fluidization units, preferably radially extending fluidization units, and combinations thereof. More preferably the pyrolysis reactor PR is selected from reactors comprising a reactor chamber and a rotation mechanism, wherein said rotation mechanism is selected from the group comprising or preferably consisting of conveyor screws, conveyor double screws, kneaders, hammer mills, fluidization units, preferably radially extending fluidization units, and combinations thereof. In one aspect of the present invention, two pyrolysis reactors (PR1 and PR2) are fluidically connected to each other whereby the second pyrolysis reactor PR2 is downstream of the first pyrolysis reactor PR1. Preferably, the pyrolysis is performed in the pyrolysis reactor PR under an inert atmosphere exempt of oxygen or air. 240644W001

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[0156] Optionally, a co-feedstock OF is provided for step (viii) and in addition to the separated reaction residue SRR and / or the dried separated reaction residue DSRR, preferably the dried separated reaction residue DSRR fed into the pyrolysis reactor PR. Said optional co-feedstock OF comprises waste such as plastic waste (e.g., mixed plastic waste (MPW), end-of-life tires (ELT)), bio waste, and mixtures thereof. Preferably said optional cofeedstock OF comprises plastic waste. In the context of the present invention, the term “plastic waste” refers to any plastic material discarded after use, i.e., the plastic material has reached the end of its useful life and is considered post-consumer waste and plastic material comprised in industrial waste such as production waste of plastic material. The plastic waste can be pure polymeric plastic waste, mixed plastic waste or film waste, including soiling, adhesive materials, fillers, residues etc. Content optionally comprised in plastic waste which is not subjected to a pyrolysis reaction (e.g., inorganic fillers such as silica particles, carbon particles, glass fibers and the like) are defined as “inerts” herein. The plastic waste may have an oxygen content, a nitrogen content, sulfur content, halogen content and optionally also a heavy metal content. The plastic waste can originate from any plastic material containing source. Accordingly, the term “plastic waste” includes industrial and domestic plastic waste and including used tires and agricultural and horticultural plastic material. The term “plastic waste” also includes used petroleum-based hydrocarbon material such as used motor oil, machine oil, greases, waxes, etc.

[0157] Typically, plastic waste is a mixture of different plastic materials, including hydrocarbon plastics, e.g., polyolefins such as polyethylene (HDPE, LDPE) and polypropylene, polystyrene, copolymers comprising polystyrene, and polymers composed of carbon, hydrogen, and other elements such as chlorine, fluorine, oxygen, nitrogen, sulfur, silicone, etc., for example chlorinated plastics, such as polyvinylchloride (PVC), polyvinylidene chloride (PVDC), etc., nitrogen-containing plastics, such as polyamides (PA), polyurethanes (PU), acrylonitrile butadiene styrene (ABS), etc., oxygen-containing plastics such as polyesters, e.g., polyethylene terephthalate (PET), polycarbonate (PC), etc., and rubbers such as sulfur bridge crosslinked rubbers. More preferably, waste is mixed plastic waste (MPW) and comprises at least two members of the group comprising or preferably consisting of polyolefins, polystyrene, copolymers comprising polystyrene, polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyamides (PA), polyurethanes (PU), polyesters, polycarbonate (PC), and rubbers.

[0158] Typically, the plastic material comprises additives, such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, antioxidants, etc. These additives may comprise elements other than carbon and hydrogen. For example, bromine is mainly found in connection to flame retardants. Heavy metal compounds may be used as lightfast pigments and / or stabilizers in plastics. Cadmium, zinc, and lead may be present in heat stabilizers and slip agents used in plastics manufacturing. The plastic waste can also contain residues. Residues in the sense of the invention are contaminants adhering to the plastic waste. The additives and residues are usually present in an amount of less than 50 wt.-%, preferably less than 30 wt.-%, more preferably less than 20 wt.-%, even more preferably less than 10 wt.-%, based on the total weight of the dry weight plastic. 240644W001

[0159] 18

[0160] Examples of rubber waste (which is also considered “plastic waste” in the sense of the present invention) include end-of-life tires, rubber waste produced during manufacturing processes and discarded rubber containing products such as latex examining gloves and gaskets. End-of-life tires comprise further ingredients such as textiles and organic and inorganic additives which may be separated from the rubber portion of end-of-life tires prior to pyrolysis. Pyrolysis oils obtained by pyrolysis of (predominantly) end-of-life tires are also known as tire pyrolysis oils (TPO).

[0161] Bio waste comprises green waste, food waste, human waste, manure, sewage, sewage sludge, wood, agricultural waste, and slaughterhouse waste.

[0162] Optionally, said optional co-feedstock OF is pretreated before provided for optional step (viii). Preferably, the optional co-feedstock OF is pretreated by a method selected from the group comprising or preferably consisting of sorting, comminution, preheating, solvolysis, and combinations thereof. Such an optional pretreatment can for example increase the yield of the pyrolysis oil PO and / or result in a more economic first pyrolysis reaction in optional step (viii). For example, when applying sorting, the amount of more preferred plastic wase such as plastic waste having a high concentration of polyolefins and a low concentration of inerts can be archived which results in a higher yield of pyrolysis oil PO. Comminution may reduce the temperature required in optional step (viii) and thereby to a reduced amount of thermal energy required for optional step (viii). Preheating the optional cofeedstock CF, preferably to a temperature in the range of 200 to 360 °C can also reduce the thermal energy required in optional step (viii). Furthermore, such a preheating can reduce the amount of undesired chlorine which may be present in the optional co-feedstock CF (e.g., in the form of a chlorinated polymer such as PVC). At least a portion of chlorine is removed in the form HCI during such an optional preheating.

[0163] Furthermore, the optional co-feedstock CF can be homogenized with the separated reaction residue SRR and / or the dried separated reaction residue DSRR during preheating which results in a more uniform pyrolysis reaction in step (viii).

[0164] Optionally, at least a portion of the pyrolysis oil PO may be subjected to a steam cracking process in a steam cracking plant whereby C2-C4 olefins and C6-C8 aromatic hydrocarbons are formed.

[0165] Next, the at least one member selected from the group consisting of separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO and combinations thereof is / are subjected in step (ix) to a gasification process wherein said gasification process comprises at least one gasifier G and whereby a gas stream GS1 is formed. Said gas stream GS1 comprises CO, H2and CO2.

[0166] The molar ratio CO : H2in the gas stream GS1 formed in step (ix) preferably ranges from 0.5 : 1 to 1 : 0.5, more preferably from 0.8 : 1 to 1 : 0.8 and most preferably is about 1 : 1. The gas stream GS1 formed in step (ix) preferably comprises < 15 Vol.-% CO2, more preferably < 10 Vol.-% CO2and most preferably < 8 Vol.-% CO2. 240644W001

[0167] 19

[0168] The at least one gasifier G has at least one inlet through which the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof is / are fed into said at least one gasifier G and at least one outlet through which the gas stream GS1 is purged from said at least one gasifier G. Preferably, the at least one gasifier G has more than one inlet. Thereby, more than one feedstock can be fed into the at least one gasifier G through separate inlets. The term “inlet” comprises openings in the at least one gasifier G such as flaps and locks but also annual gaps as part of a burner such as in twin fluid atomizers, pressure nozzles and pressure atomizers.

[0169] Optionally, at least one co-feedstock OF' is provided and subjected together with the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof to a gasification process in at least one gasifier G in step (ix). The meaning of “together” depends on the kind of the at least one optional co-feedstock OF' and the type of gasifier G employed in step (ix) and is explained in detail below.

[0170] Preferably, the at least one optional co-feedstock OF' is selected from the group comprising biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end of life tires, pyrolysis oils made from biomass, heating oils, vacuum residues, preferably vacuum distillation residues, crude oil residues, heavy crude oils, extra heavy crude oils, tar sand bitumen, visbreaker bottom residues, deasphalter bottom residues, 05 asphalthene fraction, high viscous residues, fuel oils, pyrolysis gasolines, waste oils, wastewater, used oils, municipal solid waste (MSW), automotive shredder residue (ASR), coal, natural gas, industrial waste streams from other chemical processes than production of polymer dispersions, CO2 and mixtures thereof.

[0171] More preferably, the at least one optional co-feedstock OF' is selected from the group consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end-of-life tires, pyrolysis oils made from biomass, municipal solid waste (MSW), automotive shredder residue (ASR), CO2and mixtures thereof.

[0172] The term “biomass” includes but is not limited to wood, wood pellets, wood chips, straw, lignocellulosic biomass, energy crops, algae, bio-based oils, and bio-based fats (preferably hydrated).

[0173] Biomass is preferably torrefied or converted by pyrolysis into a pyrolysis oil before used in step (ix) as an optional co-feedstock OF'. Municipal solid waste (MSW) is optionally pre-treated by methods such as drying, shredding, sorting, inert removal and preferably used in step (ix) in form of refuse-derived fuel (RDF) before used in step (ix) as optional co-feedstock OF'. Shredder residues such as automotive shredder residue (ASR) is preferably pre-treated by methods such as sorting, metal removal and the like before used in step (ix) as optional co-feedstock OF'. Furthermore, torrefied biomass is preferably pre-heated to a temperature such as 200 °C before fed into a gasifier G as optional co-feedstock OF' in step (ix). 240644W001

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[0175] Liquid optional co-feedstocks OF' such as bio-based oils and pyrolysis oils are preferably pre-heated and / or pressurized before fed into the gasifier G in step (ix). In case the gasifier G is a plasma gasifier, the liquid optional co-feedstock OF' is preferably pressurized to > 1 bar(abs.), more preferably to > 2 bar(abs.) and most preferably to about 4 bar(abs.) before fed into the gasifier G in step (ix). In case the gasifier G is an entrained flow gasifier, the liquid optional co-feedstock OF' is preferably pressurized to > 10 bar(abs.), more preferably > 20 bar(abs.) and most preferably > 40 bar(abs.) before fed into the gasifier G in step (ix).

[0176] Suitable means for pre-heating and / or pressurizing liquid feedstocks (including the pyrolysis oil PO obtained in optional step (viii)) for feeding into a gasifier are known in the art, comprise for example flaps and locks but also annual gaps as part of a burner such as in twin fluid atomizers, pressure nozzles and pressure atomizers, and can be adapted to a given optional co-feedstock OF' and / or gasifier G type by the skilled person.

[0177] In case the gasifier G is an entrained flow gasifier, solid optional co-feedstocks CF' such as municipal solid waste (MSW), refuse-derived fuel (RDF), wood chips, wood pellets and the like, said further feedstock is preferably pressurized e.g., in a lock before fed into the gasifier G in step (ix).

[0178] The at least one gasifier G is selected from entrained flow gasifiers and plasma gasifiers. Preferably, the at least one gasifier G is a plasma gasifier. More preferably, the at least one gasifier G is a plasma fixed-bed gasifier.

[0179] An overview of gasifiers G is for example provided in James G. Speight, Handbook of Gasification Technology, Scrivener Publishing and Wiley, 2020, chapter 8.4.2, pages 259 to 262.

[0180] The optional co-feedstock CF' is preferably fed separately into the gasifier G, i.e., not mixed with the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof before being fed into the gasifier G. Thereby, variations in mass flow, calorific value and other properties of the separated reaction residue SRR, dried separated reaction residue DSRR pyrolysis oil PO or combinations thereof can be better balanced and as a result a steady operation of the gasifier G maintained. The optional co-feedstock OF' is preferably fed into the gasifier G by means preferably selected from lock, screw conveyor, hopper, and flap.

[0181] Most preferably, the optional co-feedstock OF' is selected from the group consisting of torrefied biomass, pyrolysis oil, bio-based oils, CO2 and mixtures thereof, wherein the pyrolysis oil is manufactured by pyrolysis from mixed plastic waste (MPW), end of life tires (ELT) and biomass. Such optional co-feedstocks CF' have more homogenized properties such as calorific value compared to, for example, municipal solid waste (MSW).

[0182] In one aspect of the present invention, a CO2 waste stream from one or more chemical processes such as CO2 capture by absorption is also co-fed into the at least one gasifier G. 240644W001

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[0184] Solid fuel particles are injected into an entrained flow gasifier G in a high-velocity stream of gas and are heated to high temperatures (typically between 850 and 1400 °C) in the presence of oxygen and / or steam. The solid particles are provided by the optional co-feedstock OF' and / or said separated reaction residue SRR and / or dried separated reaction residue DSRR are preferably transported in downdraft mode.

[0185] In case the at least one gasifier G in step (ix) is an entrained flow gasifier, the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof are preferably compressed up to 40 bar(abs.) or higher before fed into the at least one gasifier G.

[0186] The temperature inside the entrained flow gasifier G preferably ranges from 1000 to 1500 °C, more preferably from 1100 to 1450 °C and most preferably from 1200 to 1400 °C. The pressure inside the entrained flow gasifier preferably ranges from 1 to 55 bar(abs.), more preferably from 5 to 50 bar(abs.) and most preferably from 20 to 45 bar(abs.).

[0187] Addition of at least one optional co-feedstock OF' is preferred because thereby the desired constant operation conditions in the entrained flow gasifier can be maintained and synthesis gas having the desired molar ratio CO : H2 is formed.

[0188] The weight ratio (separated reaction residue SRR and / or pyrolysis oil PO and / or dried separated reaction residue DSRR) : (further feedstock OF') preferably ranges from 1 : 1 to 1 : 10, more preferably from 1 : 2 to 1 : W and most preferably from 1 : 5 to 1 : 10.

[0189] The weight ratio “(separated reaction residue SRR and / or pyrolysis oil PO and / or dried separated reaction residue DSRR, and optionally co-fed further feedstock OF') : steam” preferably ranges from 1 : 1 to 10 : 1, more preferably from 2 : 1 to 10 : 1 and most preferably from 5 : 1 to 10 : 1 or higher

[0190] Preferably, the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof, and the at least one optional co-feedstock OF' are fed into the entrained flow gasifier via at least one burner whereby said at least one burner comprises one annular gap for the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof, and a separate annular gap through which the optional at least one co-feedstock OF' is fed. Steam, preferably mixed with oxygen is cofed into the entrained flow gasifier through a separate annular gap in said at least one burner.

[0191] Plasma gasification is a high-temperature waste treatment process that uses plasma, a gas composed of highly charged particles, to break down organic matter into a gas. In this process, the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof is / are fed into a plasma reactor. Preferably, the plasma is generated with at least one plasma torch, more preferably, the plasma is generated by means of at least two plasma torches. Most preferably, the plasma gasifier comprises one to three plasma 240644W001

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[0193] torches in the part of the gasifier where the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof is / are fed onto the plasma gasifier and one or two plasma torches in the part of the plasma gasifier where the gas stream GS1 leaves the plasma gasifier (most preferably in arrangement which forces the gas stream GS1 to pass said one or two plasma torches). The high temperatures inside the plasma gasifier, which can reach up to about 10000 K, cause the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof to vaporize and break down into the constituent components CO, H2and CO2.

[0194] In case the at least one gasifier G in step (ix) is a plasma gasifier, the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof is / are preferably compressed up to 4 bar(abs.) before fed into the at least one gasifier G.

[0195] The temperature of the gas leaving the plasma gasifier is preferably in the range of 1100 to 1400 °C, most preferably around 1300 °C. The pressure of the gas leaving the plasma gasifier is preferably at least 0.7 bar(abs.) and more preferably at least 1 bar(abs.). The residence time of the reactants inside the plasma gasifier is at least 2 to 3 s. The plasma is preferably generated from a gas selected from the group comprising steam, CO2, O2, air and mixtures thereof. More preferably, the plasma is generated from steam, CO2or a mixture of steam and CO2.

[0196] The separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO or combinations thereof is / are preferably fed into the plasma gasifier through an opening separate of the opening through which the at least one optional co-feedstock OF' is fed. Steam is preferably fed to the plasma gasifier through still another opening.

[0197] The amount of CO2formed in step (ix) can be further reduced or the emission can be even reduced to zero in case the CO2formed in step (ix) is co-fed into the at least one gasifier G as a co-feedstock CF'. Thereby, CO2is converted into CO. Processes utilizing CO2as co-feedstock suited for gasification in at least one gasifier G are for example described in WO 2022 / 200532 A1.

[0198] The process according to the present invention comprises a further step (x) wherein said gas stream GS1 is cleaned and thereby a gas stream GS2 is formed. Preferably, said step (x) comprises, in this order, cleaning gas stream GS1 and thereby forming gas stream GS2, and further, separating H2and CO in gas stream GS2 and compressing at least one of H2and CO separated from gas stream GS2.

[0199] Typical impurities in the gas stream GS1 comprise chlorides, sulfur-containing organic compounds such as sulfur dioxide, trace heavy metals (e.g., as respective salts), tars, condensable hydrocarbons and particulate residues. Various chemical and / or physical methods for removal of such impurities from said gas stream GS1 such as filtration, scrubbing, condensation and ab- / adsorption are known and can be chosen and adapted according to the type and respective concentration of the impurities in said gas stream GS1 and the tolerance to such 240644W001

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[0201] impurities in a further process FP1. Some selected methods for removal of impurities from said gas stream GS1 will be discussed in more detail. One or more of said methods can also be implemented into the optional gas treatment unit GTU. However, this selection of methods does not limit the scope of the present invention.

[0202] Other gaseous substances such as HOI and H2S are formed and / or separated from the gas stream GS1 in the optional gas treatment unit GTU. The impurities are removed from the gas stream GS1 and a gas stream GS2 having a first molar ratio H2 : CO is obtained.

[0203] Particulate impurities can be removed from the gas stream GS1 by a cyclone and / or filters, chlorides by wet scrubbing, trace heavy metals, catalytic hydrolysis for converting sulfur-containing organic compounds to H2S and acid gas removal for extracting sulfur-containing gases such as H2S. Bulky and (fine) particles such as dust in the gas stream GS1 may also be removed with a quench in a soot water washing unit.

[0204] Particulate impurities can be optionally removed from the gas stream GS1 directly by a cyclone and / or filters after the gas stream GS1 leaves the gasifier. Hence, the removal of particles from the gas stream GS1 can be part of a gasifier and / or part of the optional gas treatment unit GTU which is fluidically connected to the at least one gasifiers G.

[0205] Fine particles can be optionally removed from the raw synthesis gas directly with filters after the gas stream GS1 leaves the at least one gasifier G. Hence, the removal of fine particles from the gas stream GS1 can be part of the at least one gasifier G and / or part of the optional gas treatment unit GTU which is fluidically connected to the at least one gasifier G.

[0206] The optional gas treatment unit GTU preferably comprises a washing unit for removing CO2from the gas stream GS1. Most preferably, said washing unit is an “amine wash” or a “methanol” wash which uses one or more amine compounds such as alkanolamines or methanol to absorb CO2. Such washing units are known in the art and can be adapted for removal of CO2 from a gaseous stream GS1 by the skilled person.

[0207] CO and / or H2 are optionally separated from the gas stream GS1. CO can be separated from the gas stream GS1 in a synthesis gas separation unit which is, optionally, downstream of and fluidically connected to the at least one gasifier G. CO can be separated from gas stream GS1 by cryogenic separation methods, commonly referred to as a “cold box” which makes use of the different boiling points of CO and H2. H2 can be separated using H2-selective membranes thorough which H2 permeates and is thereby separated from the GS1 stream.

[0208] The gas stream GS1 has a first molar ratio H2 : CO. Optionally, the gas stream GS1 is then preferably subjected to a water-gas shift reaction in a water-gas shift unit. Thereby, the H2 content in the gas stream GS1 is increased by reacting a portion of the CO of the gas stream GS1 with water to form additional H2 and CO2 and thereby gas stream GS2 having a second molar ratio H2 : CO is formed and leaves the water-gas shift unit. The H2 content in 240644W001

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[0210] said gas stream GS2 leaving the water-gas shift unit and having a second molar ratio H2 : CO is higher than in said gas stream GS1 leaving the at least one gasifier having a first molar ratio H2 : CO. The hydrogen content in gas stream GS1 can for example also be increased by adding hydrogen provided by another source such as hydrogen formed by electrolysis of water, preferably using electrical energy from a renewable source such as solar and / or wind energy.

[0211] The water-gas shift reaction will operate with a variety of catalysts (such as copper-zinc-aluminum catalysts and chromium or copper promoted iron-based catalysts) in the temperature range between about 200 °C and about 480 °C.

[0212] The gas stream GS2 is optionally compressed, preferably, in case the separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PC or combinations thereof were / was converted to gas stream GS1 in a plasma gasifier. In this case, gas stream GS2 is preferably compressed to a pressure in the range 1.5 to 4 bar(abs.).

[0213] Optionally, the gas stream GS1 and / or the gas stream GS2 are / is then subjected to a further process FP1 selected from the group comprising methanization, alcohol synthesis (preferably methanol synthesis) and Fischer-Tropsch synthesis whereby at least one first product stream PS1 is formed. The gas stream GS2 can also be used as a fuel gas Said optional further processes FP1 are briefly described below:

[0214] Optionally, the gas stream gas stream GS2 can be converted into methane by a methanation reaction. The methanation reaction is described by chemical reaction schemes (1) and (2):

[0215] CO + 3H2-> CH4 + H2O (1)

[0216] CO2+ 4H2-> CH4+ 2H2O (2)

[0217] The methanation reaction and suitable methanation units are for example described in S. Rbnsch, J. Schneider, S. Matthischke, M. Schluter, M. Gbtz, J. Lefebvre, P. Prabhakaran, S. Bajohr: Review on methanation - From fundamentals to current projects; Fuel 166 (2016) 276-296 and can be selected and adapted by the skilled person.

[0218] The methanation reaction is for example a catalytic reaction using nickel on alumina catalysts, preferably a honeycomb shape catalyst, at 1 to 70 bar and 200 to 700 °C, preferably 5 to 60 bar, more preferably 10 to 45 bar and preferably 200 to 550 °C, more preferably 10 to 45 bar.

[0219] Alcohols such as methanol are another chemical product which can be manufactured from the gas stream GS2 by an optional further process FP1. The most preferred, methanol, is produced from synthesis gas by a catalytic gas phase reaction at about 5 to 10 MPa and a temperature of about 200 to about 300 °C using a catalyst in a 240644W001

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[0221] low-pressure methanol process in e.g., adiabatic reactors or quasi-isothermal reactors. The catalyst is for example a mixture of copper and zinc oxides, supported on alumina. The methanol synthesis and various options thereof suitable to be combined with the production system according to the present invention are disclosed in Ullmann's Encyclopedia of Industrial Chemistry (2012), Chapter “Methanol”, p. 3 to 12.

[0222] The gas stream GS2 can also optionally be converted into hydrocarbons such as light synthetic crude oil in an optional Fischer-Tropsch (FT) reaction unit by the FT process. Such hydrocarbons are also denoted “Fischer-Tropsch hydrocarbons”. The light synthetic oil can be further converted by hydrocracking and / or isomerization to naphtha, light olefins, or diesel fuel. For production of gasoline and light olefins, the FT process is operated in a temperature range of about 330 to about 350 °C and a pressure of about 2.5 MPa (high-temperature FT-process), for production of waxes and / or diesel fuel, in a temperature range of about 220 to about 250 °C and a pressure of about 2.5 to about 4.4 MPa (low-temperature FT-process). Suitable reactors for low-temperature FT-processes comprise tubular fixed-bed reactors and slurry bed reactors. Suitable reactors for high-temperature FT-processes comprise circulating fluidized-bed reactors and SAS (Sasol advanced synthol) reactors. Iron- and / or cobalt-based catalysts are used for the FT-process. The Fischer-Tropsch synthesis and various options thereof suitable to be combined with the production system according to the present invention are disclosed in Ullmann's Encyclopedia of Industrial Chemistry (2012), Chapter “Coal Liquefaction”, p. 20 to 33.

[0223] In one aspect of the present invention, the gas stream GS2 is converted into methanol for example by a method described above. Next, the methanol is converted into propene by a methanol-to-propene (MTP) synthesis which are for example disclosed in M. Khanmohammadi, Sh. Amani, A. Bagheri Garmarudi, A. Niaei “Methanol-to-propylene process: Perspective of the most important catalysts and their behavior” Chinese Journal of Catalysis 37 (2016) 325-339 (DOI: 10.1016 / S 1872-2067(15)61031 -2). Next, the propene is used as the C3feedstock in an acrylic acid synthesis unit and converted into crude acrylic acid as described above. The acrylic acid can then be converted into a monomer M. Accordingly, in this aspect of the present invention, reaction residues RR are utilized as a feedstock for the manufacture of monomers M.

[0224] The cleaned synthesis gas (gas stream GS2) is then preferably used in a process for producing an aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, where at least a portion of said monomers M to be polymerized are monomers M produced from gas stream GS2 as the raw material or one of the raw materials, which synthesis gas is obtained by gasification of at least one waste stream from a production plant for aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M. Accordingly, the reaction residues RR of said process are converted into feedstock(s) for said process. A closed-loop recycling is archived thereby.

[0225] In particular, the synthesis gas is then optionally used in the production of methanol which is subsequently used in the production of the ethylenically unsaturated monomers M, e.g., by the so-called MTO route (methanol to olefins). Further details about MTO processes are disclosed in Makarand R. Gogate (2019) Methanol-to-olefins 240644W001

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[0227] process technology: current status and future prospects, Petroleum Science and Technology, 37:5, 559-565, DOI: 10.1080 / 10916466.2018.1555589 and the literature mentioned therein. A portion of that synthesis gasbased methanol may also be converted into alkanes, olefins, oxygenates, and alcohols. These chemicals can be blended into, or used directly as, diesel fuel, gasoline, and other liquid fuels.

[0228] Routes from synthesis gas (gas stream GS2) to monomers M further comprise:

[0229] (a) the synthesis gas fraction, which is in particular used in the production of methanol, which itself is used in the production of methyl methacrylate;

[0230] (b) a C2-C4-olefine fraction (at least a portion thereof manufactured from gas stream GS2 via methanol and MTO) and the synthesis gas fraction, which is in particular used for the production of methacrylic acid, methyl methacrylate, vinyl acetate, vinyl propionate and vinyl esters of Koch acids;

[0231] (c) a C2-C4-olefine fraction, a >64 olefin fraction and the synthesis gas fraction which is used for the production of C5-C10 alkylesters of acrylic acid and C5-C10 alkylesters of methacrylic acid.

[0232] Further manufacturing routes starting from gas stream GS2 (synthesis gas) of other ethylen ically unsaturated monomers M, such as styrene, divinylbenzene, acrylic acid, methacrylic acid, methyl methacrylate and alkyl acrylates are disclosed in WO 2024 / 056515 A1.

[0233] The present invention further concerns a production plant for aqueous polymer dispersions comprising an integrated waste stream treatment facility, wherein said production plant comprises

[0234] (i) at least one reactor R,

[0235] (ii) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R,

[0236] (iii) a means MC for collecting reaction residue loaded water RRLW, said means MO downstream of and fluidically connected to said at least one reactor R and / or said at least one vessel V,

[0237] (iv) at least one further means MS for separating the reaction residue RR from said reaction residue loaded water RRLW and optionally drying the reaction residue RR separated form said reaction residue loaded water RRLW and

[0238] (v) at least one gasifier G, said at least one gasifier G downstream of and directly or indirectly fluidically connected to said means MS

[0239] or at least one pyrolysis reactor PR, said at least one pyrolysis reactor PR downstream of and directly or indirectly fluidically connected to said means MS.

[0240] The means MC for collecting reaction residue loaded water RRLW can be a simple storage tank or a pit for collecting the reaction residue loaded water RRLW.

[0241] The means MS is suited for separating the reaction residue RR from the reaction residue loaded water RRLW, by a method selected from the group comprising or preferably consisting of adding at least one type 1 additive to 240644W001

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[0243] said reaction residue loaded water RRLW, adding at least one type 2 additive to said reaction residue loaded water RRLW, changing the pH value of said reaction residue loaded water RRLW, mechanical shearing of said reaction residue loaded water RRLW, electrical coagulation of said reaction residue loaded water RRLW, and combinations thereof. Combinations can be of any order, e.g., first adding a type 1 additive, then changing the pH value of the reaction residue loaded water RRLW, or first changing the pH value of the reaction residue loaded water RRLW and then adding a type 1 additive, and preferably then drying said separated reaction residue SRR to form the dried separated reaction residue DSRR.

[0244] “Directly” is defined as fluidically connected by a suitable means such as a pipe. Accordingly, the means MS is fluidically connected by a suitable means such as a pipe with at least one gasifier G or the means MS is fluidically connected by a suitable means such as a pipe with at least one optional pyrolysis reactor PR.

[0245] “Indirectly” is defined as interrupted by e.g., an additional unit for pre-treating the separated reaction residue SRR or the dried separated reaction residue (e.g., by a comminution method), storage tank(s), transporting the separated reaction residue SRR or the dried separated reaction residue from a production plant for aqueous polymer dispersions to the at least one gasifier G or the at least one pyrolysis reactor PR by truck or train.

[0246] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The process of any of embodiments 1 to 3", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any of embodiments 1 , 2 and 3". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and thus, suitably supports the claims of the present invention.

[0247] 1. Process for utilizing at least one waste stream from a production plant for polymer dispersions from at least one type of monomer M, wherein said production plant comprises

[0248] a) at least one reactor R,

[0249] b) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R, and

[0250] c) a means MO for collecting reaction residue loaded water RRLW,

[0251] and wherein the process comprises the steps

[0252] (i) providing at least one type of monomer M, wherein said at least one type of monomer M is an ethylenically unsaturated monomer selected from the group consisting of monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylate esters, methacrylate esters, acrylic acid, methacrylic acid, amides of acrylic acid, amides of methacrylic acid, acrylonitrile, vinyl esters of C2-Ci2-alkanoic acids, allyl esters of C2-Ci2-alkanoic acids and mixtures thereof, 240644W001

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[0254] (ii) producing by a polymerization reaction from said at least one type of monomer M at least one reaction product RP in said at least one reactor R whereby also reaction residues RR are formed, (iii) optionally transferring said at least one reaction product RP and at least a portion of said reaction residues RR from said at least one reactor R into said at least one vessel V,

[0255] (iv) removing said at least one reaction product RP from said at least one reactor R and / or said at least one optional vessel V,

[0256] (v) providing water W to said at least one reactor R and / or said at least one optional vessel V and cleaning said at least one reactor R and / or said at least one optional vessel V with said water W, (vi) removing at least a portion of said reaction residues RR from said at least one reactor R and / or said at least one vessel V with said water W whereby reaction residue loaded water RRLW is formed,

[0257] (vii) separating said reaction residue RR from said reaction residue loaded water RRLW and thereby forming a separated reaction residue SRR, and optionally drying said separated reaction residue SRR and thereby forming a dried separated reaction residue DSRR,

[0258] (viii) optionally subjecting said separated reaction residues SRR and / or said dried separated reaction residue DSRR to a pyrolysis reaction and thereby forming a pyrolysis oil PO,

[0259] (ix) subjecting at least one member selected from the group consisting of separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO and combinations thereof to a partial oxidation reaction in at least one gasifier G and thereby forming a gas stream GS1, said gas stream GS1 comprising CO, H2 and CO2 and

[0260] (x) cleaning said gas stream GS1 and thereby forming a gas stream GS2.

[0261] 2. Process according to embodiment 1 wherein the at least one reaction product RP is an aqueous polymer dispersion formed by radical aqueous emulsion polymerization of at least one type of monomer M.

[0262] 3. Process according to embodiment 1 or 2 wherein the at least one type of monomer M to be polymerized comprise at least 80% by weight, based on the total weight of the at least one type of monomer M, one of the following monomer combinations (1) to (5):

[0263] (1) at least one monovinyl aromatic monomer, at least one acrylate ester and optionally one or more methacrylate esters,

[0264] (2) at least one acrylate ester and at least one methacrylate ester,

[0265] (3) at least one monovinyl aromatic monomer, butadiene and optionally one or more monomers selected from acrylate esters and methacrylate esters

[0266] (4) at least one vinylester of a C2-Ci2-alkanoic acid;

[0267] (5) at least one vinylester of a C2-Ci2-alkanoic acid and at least one C2-C4-olefine. 240644W001

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[0269] 4. Process according to any one of embodiments 1 to 3 wherein the acrylate esters are selected from C1-C18 alkyl acrylates and C5-C18 cycloalkyl acrylates and where the methacrylate esters are selected from C1-C18 alkyl methacrylates and C5-C18 cycloalkyl methacrylates.

[0270] 5. Process according to any one of embodiments 1 to 5 wherein the at least one reactor R is selected from the group comprising or preferably consisting of stirrer tank reactor, continuously operated tubular reactors with and without internal mixing elements.

[0271] 6. Process according to any one of embodiments 1 to 6 wherein said at least one reaction product RP is selected from the group comprising or preferably consisting of aqueous polymer dispersions, aqueous polymer solutions and aqueous polymer suspensions.

[0272] 7. Process according to any one of embodiments 1 to 7 wherein at least a portion of said reaction residues RR are removed from said at least one reactor R and optionally from said at least one optional vessel V.

[0273] 8. Process according to any one of embodiments 1 to 8 wherein the reaction residue RR is separated from said reaction residue loaded water RRLW by at least one of the following steps: adding at least one type 1 additive to said reaction residue loaded water RRLW, adding at least one type 2 additive to said reaction residue loaded water RRLW, changing the pH value of said reaction residue loaded water RRLW, mechanical shearing of said reaction residue loaded water RRLW, electrical coagulation of said reaction residue loaded water RRLW, and combinations thereof.

[0274] 9. Process according to embodiment 8 wherein the at least one type 1 additive is selected from metal salts.

[0275] 10. Process according to embodiment 8 or 9 wherein the at least one type 1 additive is is selected from the group comprising or preferably consisting of aluminum sulfate, ferric chloride, aluminium chloride, polyaluminium chloride (PAC), ferric sulfate and combinations thereof.

[0276] 11. Process according to any one of embodiments 8 to 10 wherein the at least one type 2 additive is selected from homo- or copolymers, either linear or branched, said homo- or copolymers comprising at least one building unit selected from the group comprising or preferably consisting of acrylamide, acrylic acid, dimethylamine, methacrylamide, N-vinylformamide, vinylamine, methacrylic acid, acrylonitrile, and vinyl acetate.

[0277] 12. Process according to any one of embodiments 8 to 11 wherein the at least one type 2 additive is selected from the group comprising or preferably consisting of polyacrylamide, polyvinylamine, polyethylenimine and combinations thereof. 240644W001

[0278] 30

[0279] 13. Process according to any one of embodiments 8 to 12 wherein the pH value of said reaction residue loaded water RRLW is changed by adding at least one inorganic substance having an acidic or alkaline pH value.

[0280] 14. Process according to any one of embodiments 1 to 13 wherein the reaction residue loaded water RRLW comprises less than 4 wt.-%, preferably 0.1 to 3 wt.-%, and more preferably 0.5 to 2 wt.-% reaction residue RR.

[0281] 15. Process according to any one of embodiments 1 to 14 wherein the reaction residue RR is separated from the reaction residue loaded water RRLW in step (vii) by a method selected from the group comprising or preferably consisting of gravity separation, filtration, centrifugation, separation with a screw press and combinations thereof.

[0282] 16. Process according to any one of embodiments 1 to 15 wherein the separated reaction residue SRR is dried with a hot gas such as hot air.

[0283] 17. Process according to any one of embodiments 1 to 16 wherein the separated reaction residue SRR is dried with at least means selected from the group comprising or consisting of belt dryer, oven cabinet, screw dryer, paddle dryer, fluidized bed dryer, kneader and combinations thereof.

[0284] 18. Process according to any one of embodiments 1 to 17 wherein dried separated reaction residue DSRR preferably comprises 10 to 20 wt.-% water W, more preferably no more than 10 wt.-% water W and most preferably no more than 7.5 wt.-% water W.

[0285] 19. Process according to any one of embodiments 1 to 18 wherein the said reaction residues RR has a) a calorific value in the range of 20 to 45 M J / kg, more preferably of 30 to 40 MJ / kg and most preferably of 35 to 40 MJ / kg,

[0286] and at least one, preferably all of the following further properties:

[0287] b) a carbon content in the range of 50 to 90 wt.-%, more preferably 70 to 90 wt.-% and most preferably 80 to 90 wt.-%,

[0288] c) a hydrogen content in the range of 5 to 15 wt.-%, more preferably 7 to 10 wt.-% and most preferably c to d wt.-%,

[0289] d) an oxygen content in the range of 0 to 40 wt.-%, more preferably 0 to 20 wt.-% and most preferably 0 to 2 wt.-%, and

[0290] e) a nitrogen content in the range of 0 to 20 wt.-%, more preferably 0 to 10 wt.-% and most preferably 0 to 2 wt.-%. 240644W001

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[0292] 20. Process according to any one of embodiments 1 to 19 wherein said separated reaction residue SRR and / or said dried separated reaction residue DSRR is pre-treated by a method selected from the group comprising or consisting of heating, grinding, mixing, pumping, pyrolyzing and combinations thereof.

[0293] 21. Process according to any one of embodiments 1 to 20 wherein optional pyrolyzing the separated reaction residue SRR and / or said dried separated reaction residue DSRR comprises the steps

[0294] (a) feeding said separated reaction residue SRR and / or said dried separated reaction residue DSRR into a pyrolysis reactor,

[0295] (p) subjecting said separated reaction residue SRR and / or said dried separated reaction residue DSRR to a pyrolysis reaction in said pyrolysis reactor and thereby forming a pyrolysis product PP, said pyrolysis product comprising a pyrolysis oil PO,

[0296] (X) separating said pyrolysis oil PO from said pyrolysis product PP.

[0297] 22. Process according to embodiment 21 further comprising in step (a): feeding at least one co-feedstock OF into a pyrolysis reactor, wherein said at least one co-feedstock OF comprises plastic waste.

[0298] 23. Process according to any one of embodiments 1 to 22 wherein said at least one gasifier G is selected from plasma gasifier and entrained flow gasifier.

[0299] 24. Process according to any one of embodiments 1 to 23 wherein the said reaction residue loaded water RRLW and / or said pyrolysis oil PO is / are subjected to a partial oxidation reactor in at least one gasifier G wherein said at least one gasifier G is an entrained-flow gasifier.

[0300] 25. Process according to any one of embodiments 1 to 24 wherein said separated reaction residue SRR and / or said dried separated reaction residue DSRR is / are subjected to a partial oxidation reactor in at least one gasifier G wherein said at least one gasifier G is fixed-bed gasifier G or a fluidized-bed gasifier G.

[0301] 26. Process according to any one of embodiments 1 to 25 wherein the gasifier G consists of two gasifiers wherein the second gasifier G is downstream of and fluidically connected to the first gasifier PG and wherein the first gasifier PG is a fixed-bed gasifier or a fluidized-bed gasifier

[0302] 27. Process according to any one of embodiments 1 to 26 wherein the at least one gasifier G is a fixed-bed plasma gasifier.

[0303] 28. Process according to any one of embodiments 1 to 27 wherein a further feedstock OF' is subjected to a partial oxidation in at least one gasifier G in step (ix). 240644W001

[0304] 32

[0305] 29. Process according to embodiment 28 wherein the further feedstock CF' is selected from the group comprising or preferably consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end of life tires, pyrolysis oils made from biomass, heating oils, vacuum residues, preferably vacuum distillation residues, crude oil residues, heavy crude oils, extra heavy crude oils, tar sand bitumen, visbreaker bottom residues, deasphalter bottom residues, C5 asphalthene fraction, high viscous residues, fuel oils, pyrolysis gasolines, tire pyrolysis oils (TPO), waste oils, wastewaters, used oils, municipal solid waste (MSW), automotive shredder residue (ASR), coal, natural gas, industrial waste streams from other chemical processes than production of polymer dispersions, CO2 and mixtures thereof.

[0306] 30. Process according to embodiment 28 or 29 wherein the weight ratio (separated reaction residue SRRR and / or pyrolysis oil PO and / or dried separated reaction residue DSRR) : (further feedstock CF') preferably ranges from 1 : 1 to 1 : 10, more preferably from 1 : 2 to 1 : 10 and most preferably from 1 : 5 to 1 : 10.

[0307] 31. Process according to any one of embodiments 1 to 30 wherein the molar ratio CO : H2 in the gas stream GS1 formed in step (ix) preferably ranges from 0.5 : 1 to 1 : 0.5, more preferably from 0.8 : 1 to 1 : 0.8 and most preferably is about 1 : 1.

[0308] 32. Process according to any one of embodiments 1 to 31 wherein the gas stream GS1 formed in step (ix) preferably comprises < 15 Vol.-% CO2, more preferably < 10 Vol.-% CO2 and most preferably < 8 Vol.-% CO2.

[0309] 33. Process according to any one of embodiments 1 to 32 wherein steam is co-fed into the at least one gasifier G in step (ix).

[0310] 34. Process according to embodiment 33 wherein the weight ratio “(separated reaction residue SRR and / or pyrolysis oil PO and / or dried separated reaction residue DSRR, and optionally co-feedstock CF') : steam” preferably ranges from 1 : 1 to 10 : 1, more preferably from 2 : 1 to 10 : 1 and most preferably from 5 : 1 to 10 : 1 or higher.

[0311] 35. Process according to any one of embodiments 1 to 34 wherein the at least one gasifier G is an entrained flow gasifier and wherein oxygen and steam are co-fed in step (ix).

[0312] 36. Process according to any one of embodiments 1 to 35 wherein the at least one gasifier G is a plasma gasifier utilizing a plasma and wherein said plasma is formed from one or more sources selected from the group comprising or consisting of steam, CO2, O2, air and mixtures thereof.

[0313] 37. Process according to embodiment 36 wherein the plasma is formed by a method selected from the group comprising or consisting of microwave radiation, electrical arc and plasma torch. 240644W001

[0314] 33

[0315] 38. Process according to embodiment 36 or 37 wherein the plasma is formed by at least one plasma torch.

[0316] 39. Process according to any one of embodiments 1 to 38, said process comprising a further step:

[0317] (xi) producing an aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein at least a portion of the monomers M to be polymerized are ethylenically unsaturated monomers M produced from gas stream GS2 as raw material or one of the raw materials.

[0318] 40. Process according to any one of embodiments 1 to 39 wherein said at least one reaction product RP is not a fluoropolymer.

[0319] 41. Process according to any one of embodiments 1 to 40 wherein the residue loaded water RRLW is not subjected to a biological treatment process such as fermentation before said reaction residue RR is separated from said reaction residue loaded water RRLW.

[0320] 42. A process for producing an aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one type of ethylenically unsaturated monomer M, wherein at least a portion of the at least one type of monomer M to be polymerized are ethylenically unsaturated monomers M produced from synthesis gas as the or one of the raw material(s), which synthesis gas is obtained by gasification of at least one waste stream from a production plant for aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one type of ethylenically unsaturated monomer M.

[0321] 43. The process according to embodiment 42 wherein the at least one monomer M is selected from the group consisting of monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylate esters, methacrylate esters, acrylic acid, methacrylic acid, amides of acrylic acid, amides of methacrylic acid, acrylonitrile, vinyl esters of C2-Ci2-alkanoic acids, allyl esters of C2-Ci2-alkanoic acids and mixtures thereof.

[0322] 44. Production plant for aqueous polymer dispersions comprising an integrated reaction residue treatment facility wherein said production plant comprises

[0323] (i) at least one reactor R,

[0324] (ii) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R,

[0325] (iii) a means MC for collecting reaction residue loaded water RRLW, said means MC downstream of and fluidically connected to said at least one reactor R and / or said at least one vessel V, 240644W001

[0326] 34

[0327] (iv) at least one further means MS for separating the reaction residue RR from said reaction residue loaded water RRLW and optionally for drying the reaction residue RR separated from said reaction residue loaded water RRLW and

[0328] (v) at least one gasifier G, said at least one gasifier G downstream of and directly or indirectly fluidically connected to said means MS

[0329] or at least one pyrolysis reactor PR, said at least one pyrolysis reactor PR downstream of and directly or indirectly fluidically connected to said means MS.

[0330] 45. Use of a production plant for aqueous polymer dispersions comprising an integrated reaction residue treatment facility according to embodiment 44 for the process according to any one of embodiments 1 to 41.

[0331] The invention will be further explained by the following non-limiting examples.

[0332] Examples

[0333] Example 1

[0334] The aqueous emulsion polymerization described in Example 5 of EP 0724663 B1 is carried out in production scale in a 50 m3reactor R by using butadiene and styrene as monomers M, respectively. The emulsion polymerization results in a reaction product RP which is an aqueous polymer dispersion. Next, the reaction product RP is removed from the reactor R. Twenty more batches of said reaction product RP are manufactured in the same reactor R by the same aqueous emulsion polymerization described in Example 5 of EP 0724663 B1. Reaction residues RR remain in said reactor R after the last batch of reaction product RP is removed from said reactor R.

[0335] Example 2

[0336] Water W is provided. Next said water W having ambient temperature is sprayed through a high-pressure cleaning device equipped with a lance comprising spray jets onto the inner wall of said reactor R with a pressure of about 400 bar. Said lance comprising spray jets is moved up and down during step (vi) and the reaction residue loaded water RRLW formed thereby is collected in a means MO for collecting reaction residue loaded water RRLW.

[0337] Example 3

[0338] Next, said reaction residue RR is separated from said reaction residue loaded water RRLW and thereby the separated reaction residue SRR is formed.

[0339] The reaction residue loaded water RRLW is homogenized by stirring. Next, sulfuric acid is added to the reaction residue loaded water RRLW and then “HM Polymin” (= type 2 additive, a product from Solenis LLC)” is added to the acidified reaction residue loaded water RRLW. The reaction residue loaded water is stirred during said process. 240644W001

[0340] 35

[0341] The reaction residue RR precipitates and is separated from the reaction residue loaded water RRLW by pumping the reaction residue loaded water RRLW to a filter press. The separated reaction residue SRR has a residual content of water W of about 50 wt.-% which is further reduced by drying separated reaction residue SRR with hot air in an oven.

[0342] Properties of the resulting dried separated reaction residue DSRR are summarized in Table 1. Said dried separated reaction residue DSRR was further used in Examples 4 to 6 as feedstock.

[0343] Table 1 : Properties of the dried separated reaction residue DSRR used as feedstock for Examples 4a to 4g and Example 5.

[0344]

[0345] Examples 4a to 4q

[0346] A portion of the dried separated reaction residue DSRR obtained in Example 3 (properties of the dried separated reaction residue DSRR are summarized in Table 1 above) was used throughout Example 4a to 4g. A gasification agent (steam) was injected into the gasifier G, enabling a plasma gasification reaction at a temperature of 1350 °C (Examples 4a to 4d) or an entrained flow gasification at 1350 °C (Examples 4e to 4g). A plasma was formed in case of plasma gasification from the inserted steam at the plasma torch outlets of the gasifier G. The plasma generation was performed by electric energy with a power given for the individual Examples. The resulting raw synthesis gas (stream GS1), comprising CO, H2O, CO2, H2and optionally ash or dust, which left the gasifier G via the gas outlet of the gasifier G was washed and dried to reduce the amount of water and ash comprised therein. Slag was removed from the gasifier G directly. After washing and drying, the gas stream GS1 had a temperature of 25 °C and was subjected to acid gas removal, by amine scrubbing, to separate acids such as CO2. The composition and normalized mass flow of the resulting gas stream GS2 is given in tables 2 and 3. 240644W001

[0347] 36

[0348] Table 2: Results from Examples 4a to 4d.

[0349] feed mass flow steam: gasifier G, GS2 composition stream: pressure mass flow el. power

[0350] temperature pressure consumption

[0351] composition temperature per kg GS2

[0352] produced

[0353] Example 4a dried 0.46 kg feed / kg GS2 0.54 kg steam / kg plasma 59.9 mol.-% H2 separated kg / h, 1 barfabs.) GS2 2.05 kWh / kg 39.6 mol.-% CO reaction 100 °C 5.4 bar (abs.) GS2 Rest: steam residue 82.6 wt.-% C 180 °C

[0354] DSRR 8.1 wt-% H

[0355] 7.9 wt-% 0

[0356] 1.0 wt-% N

[0357] 0.3 wt-% S

[0358] Example 4b dried 0.57 kg feed / kg GS2 0.488 kg plasma 56.4 mol.-% H2separated kg / h, 1 barfabs.) steam / kg GS2 1.93 kWh / kg 43.1 mol.-% C0 reaction 100 °C 5.4 barfabs.) GS2 rest: steam residue 67.9 wt.-% C 180 °C

[0359] DSRR + 5.5 wt-% H

[0360] torrefied 17.1 wt-% 0

[0361] wood10.17 wt.-% N

[0362] 0.05 wt-% S

[0363] 10.0 wt.-% ash

[0364] Example 4c dried 0.58 kg feed / kg GS2 0.49 kg steam / kg plasma 55.65 mol.-% H2separated kg / h, 1 barfabs.) GS2 1.91 kWh / kg 42.78 mol. -% CO reaction 100 °C 5.4 barfabs.) GS2 rest: steam residue 66.6 wt.-% C 180 °C

[0365] DSRR + 5.3 wt-% H

[0366] torrefied 17.1 wt-% 0

[0367] wood10.09 wt.-% N

[0368] 0.03 wt-% S

[0369] 10.9 wt-% ash

[0370] Example 4d dried 0.80 kg feed / kg GS2 0.32 kg steam / kg plasma 56.35 mol.-% H2separated kg / h, 1 barfabs.) GS2 1.94 kWh / kg 43.12 mol.-% CO reaction 100 °C 5.4 barfabs.) GS2 rest: steam residue 48.4 wt-% C 180 °C

[0371] DSRR + 6.19 wt-% H

[0372] RDF229.81 wt-% 0

[0373] 0.09 wt-% N

[0374] 0.03 wt-% S

[0375] 15.45 wt-% ash

[0376] 1: 65 wt.-% C, 5 wt.-% H, 18 wt.-% 0, 12 wt.-% ash.

[0377] 2: 45 wt.-% C, 6 wt.-% H, 32 wt.-% 0, 17 wt.-% ash. 240644W001

[0378] 37

[0379] The resulting gas stream GS2 is suited as a feedstock to produce monomers M or other utilizations, e.g., for production of methanol other further products FP1. Most of the carbon present in the reaction residues RR is converted into CO. Accordingly, the amount of CO2 produced is less than the amount produced by incineration of said reaction residue RR or combined anaerobic / aerobic fermentation.

[0380] Table 3: Results from Examples 4e to 4g.

[0381] feed mass flow Steam and gasifier G GS2 composition stream: pressure oxygen:

[0382] temperature mass flow

[0383] composition pressure

[0384] temperature

[0385] Example 4e dried 0.66 kg feed / kg GS2 0.13 kg steam / kg entrained 36.37 mol. -% H2 separated kg / h, 47 bar(abs ) GS2 flow 64.44 mol.-% CO reaction 100 °C 70 bar (abs.) gasification rest: steam residue 65.83 wt.-% C 400 °C

[0386] DSRR + 5.15 wt-% H oxygen: 0.46 kg

[0387] torrefied 17.52 wt-% 0 ?2 / ,kg,

[0388] wood10.05 wt-% N J barfabs.)

[0389] 0.014 wt.-% Sb 0

[0390] 11.43 wt-% ash

[0391] Example 4f dried 0.66 kg feed / kg GS2 0.13 kg steam / kg entrained 37.74 mol. -% H2 separated kg / h, 47 bar(abs ) GS2 flow 62.02 mol.-% CO reaction 100 °C 70 bar (abs.) gasification rest: steam residue 66.6 wt.-% C 400 °C

[0392] DSRR + 5.28 wt-% H oxygen: 0.46 kg

[0393] torrefied 17.08 wt-% 0 ?2 / kg,

[0394] wood10.09 wt-% N 47 bar(abs.)

[0395] 0.03 wt-% Sb 0

[0396] 10.9 wt.-% ash

[0397] Example 4g dried 1.06 kg feed / kg GS2 0.21 kg steam / kg entrained 31.55 mol. -% H2 separated kg / h, 47 bar(abs.) GS2 flow 68.23 mol.-% CO reaction 100 °C 70 bar (abs.) gasification rest: steam residue 47.35 wt.-% C 400 °C

[0398] DSRR + 6.13 wt-% H oxygen: 0.50 kg

[0399] RDF230.49 wt-% O 92 / kg GS2

[0400] 0.06 wt-% N J barObs.)

[0401] 0.02 wt-% Sb 0

[0402] 15.94 wt-% ash

[0403] 1: 65 wt.-% C, 5 wt.-% H, 18 wt.-% 0, 12 wt.-% ash.

[0404] 2: 45 wt.-% C, 6 wt.-% H, 32 wt.-% 0, 17 wt.-% ash.

[0405] The resulting gas stream GS2 is suited as a feedstock to produce monomers M or other utilizations, e.g., for production of methanol other further products FP1. Most of the carbon present in the reaction residues RR is converted into CO. Accordingly, the amount of CO2 produced is less than the amount produced by incineration of said reaction residue RR or combined anaerobic / aerobic fermentation. 240644W001

[0406] 38

[0407] Example 5

[0408] A portion of the dried separated reaction residue DSRR obtained from Example 3 (Table 1) was subjected to a pyrolysis reaction and thereby forming a pyrolysis oil PO.

[0409] The water content in the separated reaction residue SRR was reduced by filter pressing (residual water content of about 30 to 40 wt.-%) and then further reduced to 7.5 wt.-% by drying with hot air in an oven (Example 3) to form the dried separated reaction residue DSRR. Next, the dried separated reaction residue DSRR was comminuted with a knife to a size of about 3 to 6 mm before fed to a bench-scale pyrolysis reactor having a volume of about 0.141. The pyrolysis reactor was flushed before and during the pyrolysis reaction with nitrogen.

[0410] Next, 30 g of said dried separated reaction residue DSRR was converted by a pyrolysis reaction into a pyrolysis oil PO. The pyrolysis reaction parameters were as follows: heating to pyrolysis temperature with an average heating rate of about 15 K / min to a pyrolysis temperature T = 550 °C, held for 30 min at said pyrolysis temperature at a pressure p = 1.1 bar(abs.). The pyrolysis reactor was flushed before and during the pyrolysis reaction with nitrogen.

[0411] About 83 wt.-% of the dried separated reaction residue DSRR were converted into pyrolysis oil PO, about 3 wt.-% into char and the remaining portion into a gaseous product mixture. Said pyrolysis oil PO comprised an organic phase (87.1 wt.-% carbon, 8.9 wt.-% hydrogen, 3.5 wt.-% oxygen, 1 wt.-% nitrogen and 0.15 wt.-% sulfur) and an aqueous phase (4 wt.-% of the pyrolysis oil PO, the aqueous phase having a TOC = 7.4 wt.-%). The pyrolysis oil PO had an acid number of 12 mg KOH / g.

[0412] The pyrolysis oil PO formed in Example 5 is suited for conversion into a gas stream GS1 (and after cleaning a gas stream GS2) by a partial oxidation reaction in at least one gasifier G as shown in Examples 6a to 6d.

[0413] Examples 6a to 6d

[0414] Next, the pyrolysis oil PO manufactured in Example 5 was used as a (co-)feedstock for a partial oxidation reaction in at least one gasifier G (Examples 6a to 6d) whereby a gas stream GS1 was formed. The gasifier G was an entrained flow gasifier, and the gasification reaction was temperature of 1350 °C. The resulting raw synthesis gas (stream GS1), comprising CO, H2O, CO2, H2 and optionally ash or dust, which left the gasifier G via the gas outlet of the gasifier G was washed and dried to reduce the amount of water and ash comprised therein. Slag was removed from the gasifier G directly. After washing and drying, the gas stream GS1 had a temperature of 25 °C and was subjected to acid gas removal, by amine scrubbing, to separate acids such as CO2. The composition and normalized mass flow of the respective resulting gas stream GS2 is given in the tables below. 240644W001

[0415] 39

[0416] Table 4: Results from Examples 6a to 6d.

[0417] feed mass flow steam and gasifier G GS2 composition stream: pressure oxygen:

[0418] temperature mass flow

[0419] composition pressure

[0420] temperature

[0421] Example 6a pyrolysis oil 0.48 kg feed / kg GS2 0.10 kg steam / kg entrained 41.79 mol.-% H2 PO from kg / h, 47 bar(abs ) GS2 flow 57.24 mol.-% CO Example 5 100 °C 70 bar (abs.) gasification rest: steam 87.1 wt-% C 400 °C

[0422] 8.9 wt-% H oxygen: 0.47 kg

[0423] 35 wt -% O °2 / k9GS2

[0424] I.0 wt-% N Jbar(abs>

[0425] 0.15 wt-% Sb 0

[0426] Example 6b pyrolysis oil 0.66 kg feed / kg GS2 0.13 kg steam / kg entrained 36.97 mol.-% H2 PO from kg / h, 47 bar(abs ) GS2 flow 62.84 mol.-% CO Example 5 100 °C 70 bar (abs.) gasification rest: steam + torrefied 66.05 wt-% 0 400 °C

[0427] wood15.19 wt-% H oxygen: 0.46 kg

[0428] 1731 wt-% 0 O2 / kg GS2

[0429] 0.05 wt-% N Jbar(abs>

[0430] 0.007 wt-% Sb 0

[0431] II.43 wt-% ash

[0432] Example 6c pyrolysis oil 0.65 kg feed / kg GS2 0.13 kg steam / kg entrained 37.31 mol.-% H2 PO from kg / h, 47 bar(abs.) GS2 flow 62.47 mol.-% CO Example 5 100 °C 70 bar (abs.) gasification rest: steam + torrefied 67.01 wt-% 0 400 °C

[0433] wood15.35 wt-% H oxygen: 0.46 kg

[0434] 1668 wt-% 0 O2 / kg GS2

[0435] 0.09 wt-% N J barObs.)

[0436] 0.013 wt-% Sb 0

[0437] 10.9 wt-% ash

[0438] Example 6d pyrolysis oil 0.47 kg feed / kg GS2 0.09 kg steam / kg entrained 42.18 mol.-% H2 PO from kg / h, 47 bar(abs ) GS2 flow 56.55 mol.-% CO Example 5 100 °C 70 bar (abs.) gasification rest: steam + HVR286.88 wt-% 0 400 °C

[0439] 9.32 wt-% H oxygen: 0.48 kg

[0440] 095 wt -% O °2 / kg GS2

[0441] 0.72 wt-% N 47 bar(abs.)

[0442] 2.18 wt-% S25 C

[0443] 1: 65 wt.-% C, 5 wt.-% H, 18 wt.-% 0, 12 wt.-% ash.

[0444] 2: HVR = high viscous residue

[0445] The resulting gas stream GS2 is suited as a feedstock for the production of monomers M or other utilizations, e.g., for production of methanol other further products FP1. Most of the carbon present in the reaction residues RR is converted into CO. Accordingly, the amount of CO2 produced is less than the amount produced by incineration of said reaction residue RR or combined anaerobic / aerobic fermentation.

Claims

1. 240644W0012.403.Claims1. Process for utilizing at least one waste stream from a production plant for polymer dispersions from at least one type of monomer M, wherein said production plant comprises5.a) at least one reactor R,6.b) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R, and7.c) a means MC for collecting reaction residue loaded water RRLW,8.and wherein the process comprises the steps9.(i) providing at least one type of monomer M, wherein said at least one type of monomer M is an ethylenically unsaturated monomer selected from the group consisting of monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylate esters, methacrylate esters, acrylic acid, methacrylic acid, amides of acrylic acid, amides of methacrylic acid, acrylonitrile, vinyl esters of C2-Ci2-alkanoic acids, allyl esters of C2-Ci2-alkanoic acids and mixtures thereof, (ii) producing by a polymerization reaction from said at least one type of monomer M at least one reaction product RP in said at least one reactor R whereby also reaction residues RR are formed, (iii) optionally transferring said at least one reaction product RP and at least a portion of said reaction residues RR from said at least one reactor R into said at least one vessel V,10.(iv) removing said at least one reaction product RP from said at least one reactor R and / or said at least one optional vessel V,11.(v) providing water W to said at least one reactor R and / or said at least one optional vessel V and cleaning said at least one reactor R and / or said at least one optional vessel V with said water W , (vi) removing at least a portion of said reaction residues RR from said at least one reactor R and / or said at least one vessel V with said water W whereby reaction residue loaded water RRLW is formed,12.(vii) separating said reaction residue RR from said reaction residue loaded water RRLW and thereby forming a separated reaction residue SRR, and optionally drying said separated reaction residue SRR and thereby forming a dried separated reaction residue DSRR,13.(viii) optionally subjecting said separated reaction residue SRR and / or said dried separated reaction residue DSRR to a pyrolysis reaction and thereby forming a pyrolysis oil PO,14.(ix) subjecting at least one member selected from the group consisting of separated reaction residue SRR, dried separated reaction residue DSRR, pyrolysis oil PO and combinations thereof to a partial oxidation reaction in at least one gasifier G and thereby forming a gas stream GS1, said gas stream GS1 comprising CO, H2and CO2 and15.(x) cleaning said gas stream GS1 and thereby forming a gas stream GS2. 240644W00116.

412. Process according to claim 1 wherein the at least one type of monomer M to be polymerized comprise at least 80 % by weight, based on the total weight of the at least one type of monomer M, one of the following monomer combinations (1) to (5):18.(1) at least one monovinyl aromatic monomer, at least one acrylate ester and optionally one or more methacrylate esters,19.(2) at least one acrylate ester and at least one methacrylate ester,20.(3) at least one monovinyl aromatic monomer, butadiene and optionally one or more monomers selected from acrylate esters and methacrylate esters21.(4) at least one vinylester of a C2-Ci2-alkanoic acid;22.(5) at least one vinylester of a C2-Ci2-alkanoic acid and at least one C2-C4-olefine.

3. Process according to claim 1 or 2 wherein the acrylate esters are selected from C1-C18 alkyl acrylates and C5-C18 cycloalkyl acrylates and where the methacrylate esters are selected from C1-C18 alkyl methacrylates and C5-C18 cycloalkyl methacrylates.

4. Process according to any one of claims 1 to 3 wherein the reaction residue RR is separated from the reaction residue loaded water RRLW in step (vii) by a method selected from the group comprising or preferably consisting of gravity separation, filtration, centrifugation, separation with a screw press and combinations thereof.

5. Process according to any one of claims 1 to 4 wherein the separated reaction residue SRR is dried with at least means selected from the group comprising or consisting of belt dryer, oven cabinet, screw dryer, paddle dryer, fluidized bed dryer, kneader and combinations thereof.

6. Process according to any one of claims 1 to 5 wherein dried separated reaction residue DSRR preferably comprises 10 to 20 wt.-% water W, more preferably no more than 10 wt.-% water W and most preferably no more than 7.5 wt.-% water W.

7. Process according to any one of claims 1 to 6 wherein the said reaction residues RR has28.a) a calorific value in the range of 20 to 45 M J / kg, more preferably of 30 to 40 MJ / kg and most preferably of 35 to 40 MJ / kg,29.and at least one, preferably all of the following further properties:30.b) a carbon content in the range of 50 to 90 wt.-%, more preferably 70 to 90 wt.-% and most preferably 80 to 90 wt.-%,31.c) a hydrogen content in the range of 5 to 15 wt.-%, more preferably 7 to 10 wt.-% and most preferably c to d wt.-%,32.d) an oxygen content in the range of 0 to 40 wt.-%, more preferably 0 to 20 wt.-% and most preferably 0 to 2 wt.-%, and 240644W00133.4234.e) a nitrogen content in the range of 0 to 20 wt.-%, more preferably 0 to 10 wt.-% and most preferably 0 to 2 wt.-%.

8. Process according to any one of claims 1 to 7 wherein optional pyrolyzing the separated reaction residue SRR and / or said dried separated reaction residue DSRR comprises the steps36.(a) feeding said separated reaction residue SRR and / or said dried separated reaction residue DSRR into a pyrolysis reactor,37.(p) subjecting said separated reaction residue SRR and / or said dried separated reaction residue DSRR to a pyrolysis reaction in said pyrolysis reactor and thereby forming a pyrolysis product PP, said pyrolysis product comprising a pyrolysis oil PO,38.(X) separating said pyrolysis oil PO from said pyrolysis product PP.

9. Process according to any one of claims 1 to 8 wherein the gasifier G consists of two gasifiers wherein the second gasifier G is downstream of and fluidically connected to the first gasifier PG and wherein the first gasifier PG is a fixed-bed gasifier or a fluidized-bed gasifier10. Process according to any one of claims 1 to 9 wherein a further feedstock OF' is subjected to a partial oxidation in at least one gasifier G in step (ix).

11. Process according to claim 10 wherein the further feedstock OF' is selected from the group comprising or preferably consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end of life tires, pyrolysis oils made from biomass, heating oils, vacuum residues, preferably vacuum distillation residues, crude oil residues, heavy crude oils, extra heavy crude oils, tar sand bitumen, visbreaker bottom residues, deasphalter bottom residues, C5 asphalthene fraction, high viscous residues, fuel oils, pyrolysis gasolines, tire pyrolysis oils (TPO), waste oils, wastewaters, used oils, municipal solid waste (MSW), automotive shredder residue (ASR), coal, natural gas, industrial waste streams from other chemical processes than production of polymer dispersions, CO2and mixtures thereof.

12. Process according to claim 10 or 11 wherein the weight ratio (separated reaction residue SRRR and / or pyrolysis oil PO and / or dried separated reaction residue DSRR) : (further feedstock OF') ranges from 1 : 1 to 1 : 10, preferably from 1 : 2 to 1 : 10 and most preferably from 1 : 5 to 1 : 10.

13. Process according to any one of claims 1 to 12, said process comprising a further step:44.(xi) producing an aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one type of monomer M, wherein at least a portion of the at least one type of monomer M to be polymerized are ethylenically unsaturated monomers M produced from gas stream GS2 as raw material or one of the raw materials. 240644W00145.4314. A process for producing an aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one type of ethylenically unsaturated monomer M, wherein at least a portion of the at least one type of monomer M to be polymerized are ethylenically unsaturated monomers M produced from synthesis gas as the or one of the raw material(s), which synthesis gas is obtained by gasification of at least one waste stream from a production plant for aqueous polymer dispersion by radical aqueous emulsion polymerization of at least one type of ethylenically unsaturated monomer M.

15. Production plant for aqueous polymer dispersions comprising an integrated reaction residue treatment facility wherein said production plant comprises48.(i) at least one reactor R,49.(ii) at least one vessel V, said at least one vessel V downstream of and fluidically connected to said at least one reactor R,50.(iii) a means MC for collecting reaction residue loaded water RRLW, said means MC downstream of and fluidically connected to said at least one reactor R and / or said at least one vessel V, (iv) at least one further means MS for separating the reaction residue RR from said reaction residue loaded water RRLW and optionally for drying the reaction residue RR separated from said reaction residue loaded water RRLW and51.(v) at least one gasifier G, said at least one gasifier G downstream of and directly or indirectly fluidically connected to said means MS52.or at least one pyrolysis reactor PR, said at least one pyrolysis reactor PR downstream of and directly or indirectly fluidically connected to said means MS.

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