Flow improver for petroleum COKE slurry in gasification unit

Abstract

A liquid composition for improving the flowability and / or rheology of a coke slurry solution, comprising a lignosulfonate derivative, a surfactant and one or more synergistic additives, and methods of use thereof.

Description

FLOW IMPROVER FOR PETROLEUM COKE SLURRY IN GASIFICATION UNITCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to India Provisional Patent Application No. 202311067059, filed on October 6, 2023, which is incorporated by reference herein in its entiretyFIELD

[0002] The disclosed technology relates generally to compositions and methods for improving the flowability and / or rheology of petroleum coke slurry solutions for gasification applications. More specifically, the disclosed technology relates to compositions and methods comprising lignosulfonate derivatives, surfactants and synergistic additives for improving the flowability' and / or rheology of petroleum coke slurry solutions and for enhancing % solids loading.BACKGROUND

[0003] Difficulties in solid ammonium lignosulfonate (ALS) handling have been recognized. Because of the hardening of ALS during gasification applications, dosing and performance have been challenging to establish. Key performance indices (KPIs) of 65% solid loading with a viscosity of 600-800 cP have been challenging to meet, with 65% solid loading resulting in viscosities ranging from 1100-1200 cP. Positive displacement (PD) pumps may fail to operate against such highly viscous slurries. Alternative formulations are needed to maintain the desired viscosity of slurry solutions with targeted solid load to attain smooth pumpability' and to arrest solid and liquid phase separation.SUMMARY

[0004] The disclosed technology provides for compositions and methods for improving the flowability and / or rheology of petroleum coke slurry solutions for gasification applications.

[0005] Various aspects of the disclosure relate to a liquid composition for improving the rheology of a coke slurry solution, the composition comprising a lignosulfonate derivative.

[0006] Various aspects of the disclosure additionally relate to methods of reducing the viscosity of a coke slurry solution comprising adding to the coke slurry solution a liquid composition comprising a lignosulfonate derivative.

[0007] In various aspects, the liquid composition further comprises a surfactant and one of more synergistic additives.DETAILED DESCRIPTION

[0008] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about'’, is not limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Range limitations may be combined and / or interchanged, and such ranges are identified and include all the sub-ranges stated herein unless context or language indicates otherwise. Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions and the like, used in the specification and the claims, are to be understood as modified in all instances by the term “about”.

[0009] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.

[0010] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, or any other variation thereof, are intended to cover a nonexclusive inclusion. For example, a process, method, article or apparatus that comprises a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0011] The singular forms “a”, “an’", and “the” include plural referents unless the context clearly dictates otherwise.

[0012] The disclosed technology provides for compositions and methods for improving the flowability and / or rheology of petroleum coke slurry' solutions for gasification applications, wherein the compositions comprise lignosulfonate derivatives.

[0013] The compositions and methods disclosed herein provide at least a 30% reduction of blank petroleum coke slurry viscosity in 63-67% petroleum coke slurry solutions for gasification applications. Without being bound by theory', the compositions and methods disclosed herein may be effective in providing optimal surface coverage of petroleum coke particles and reducing interfacial tension. Without being bound by theory, due to the presence of bulk moieties of lignosulfonate salts, steric hindrance may play a crucial role when two or more lignosulfonate-coated particles approach each other. This restricts the aggregation of petroleum coke particles which may result in settling and poor flow behavior. In addition, the presence of other components in the formulation, such as surfactants, may further reduce interfacial tension which may result in releasing entrapped water in the particle core. Furthermore, certain additives, such as those disclosed herein, may act as a synergist in the performance. The disclosed compositions, when added to the petroleum coke slurry', are effective in imparting on the slurry' an optimal consistency with improved viscosity and flow behavior. The disclosed compositions are noncorrosive and provide a formulation that exhibits minimal to no foaming, minimal to no lump formation, and can easily be used to formulate petroleum coke slurry solutions characterized by a low viscosity7solution with a favorable rheology7.

[0014] As used herein, the term “coke slurry' solution” refers to a petroleum coke slurry solution. The coke slurry solution may include a solid % loading of up to a particular percentage in slurry, such as up to 67% in slurry. In various aspects, the coke slurry7solution may refer to a blank coke slurry solution, which is free from a flow7improving agent.

[0015] In various aspects of the disclosed technology, compositions for improving the flow and / or rheology7of a coke slurry7solution are disclosed. In various aspects, the composition comprises a lignosulfonate derivative. In various aspects, suitable lignosulfonate derivatives may include any lignosulfonate derivative that is effective in improving the flow and / or rheology of a coke slurry7solution. In various aspects, suitablelignosulfonate derivatives may include sodium, calcium, magnesium, and ammonium salts of lignosulfonate, and combinations thereof. In various aspects, the lignosulfonate derivative may be present in the composition in an amount of between about 30% to about 50% by weight, or about 30%, 35%, 40%, 45%, or 50% by weight, or about 35% to about 45% by weight or any concentration between any of these values.

[0016] In various aspects, the compositions may be in the form of a liquid. In various aspects, the compositions may be in the form of a liquid solution or a liquid dispersion.

[0017] In various aspects, the compositions may further include a surfactant. Suitable surfactants may include anionic surfactants, nonionic surfactants or combinations thereof. In various aspects, suitable anionic surfactants may include alkyl sulfosuccinate- based surfactants, such as dialkyl (C4-C22) sulfosuccinate, alkyl (C6-C18) aromatic sulfonates, or combinations thereof. Suitable nonionic surfactants may include ethylene oxide and propylene oxide-based tri-block co-polymers of a molecular weight ranging from 6000 to 15000 daltons, or combinations thereof. In various aspects, the surfactant may be present in the composition in an amount of between about 5% or 10% by weight, or about 5%, 6%, 7%, 8%, 9% or 10% by weight, or any concentration between any of these values. In various aspects, the nonionic surfactant may be present in the composition in an amount of between about 0.001% to 0.1% by weight, or about 0.001%, 0.005%, 0.01%, 0.05%, or 0. 1% by weight, or any concentration between any of these values.

[0018] In various aspects, the compositions may further include a synergistic additive. Suitable synergistic additives may be of high or low molecular weight, and may include mono- or polyalcohols, such as short-chain polyols selected from butoxy ethanol, butoxy ethoxy ethanol, propylene glycol, methyl substituted pentane diol, ethylene glycol, mono ethylene glycol, and combinations thereof. In various aspects, the short chain synergistic additives may be present in the composition in an amount of between about 10% to about 20% by weight, or about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% by weight, or any concentration between any of these values. Suitable synergistic additives may further include long chain polysaccharides having a molecular weight of 1,000 to 25,000 kDA, such as xanthan gum, guar gum and the like; and combinations thereof. In various aspects, the long-chain synergistic additives may bepresent in the composition in an amount of between about 0.001 to 0.05%, or about 0.001%, 0.005%. 0.01%. or 0.05%, or any concentration between any of these values.

[0019] In various aspects, a method of reducing the viscosity of a coke slurry solution is disclosed. In various aspects, the method includes adding a composition comprising a lignosulfonate derivative. In various aspects, suitable lignosulfonate derivatives may include any lignosulfonate derivative that is effective in reducing the viscosity of a coke slurry solution. In various aspects, suitable lignosulfonate derivatives may include sodium, calcium, magnesium, and ammonium salts of lignosulfonate, and combinations thereof. In various aspects, the lignosulfonate derivative may be present in the composition in an amount of between about 30% to about 50% by weight, or about 30%, 35%, 40%. 45%. or 50% by weight, or about 35% to about 45% by weight or any concentration between any of these values.

[0020] In various aspects, the composition may be in the form of a liquid. In various aspects, the composition may be in the form of a liquid solution or a liquid dispersion.

[0021] In various aspects, the compositions may further include a surfactant. Suitable surfactants may include anionic surfactants, nonionic surfactants or combinations thereof. In various aspects, suitable anionic surfactants may include alkyl sulfosuccinate- based surfactants, such as dialkyl (C4-C22) sulfosuccinate, alkyl (C6-C18) aromatic sulfonates, or combinations thereof. Suitable nonionic surfactants may include ethylene oxide and propylene oxide-based tri-block co-polymers of a molecular weight ranging from 6000 to 15000 daltons, or combinations thereof. In various aspects, the surfactant may be present in the composition in an amount of between about 5% or 10% by weight, or about 5%, 6%, 7%, 8%, 9% or 10% by weight, or any concentration between any of these values. In various aspects, the nonionic surfactant may be present in the composition in an amount of between about 0.001% to 0.1% by weight, or 0.001%, 0.005%, 0.01%, 0.05%, or 0. 1% by weight, or any concentration between any of these values.

[0022] In various aspects, the compositions may further include a synergistic additive. Suitable synergistic additives may be of high or low molecular weight, and may include mono- or polyalcohols, such as short-chain polyols selected from butoxy ethanol, butoxy ethoxy ethanol, propylene glycol, methyl substituted pentane diol, ethylene glycol, mono ethylene glycol, and combinations thereof. In various aspects, the short chainsynergistic additives may be present in the composition in an amount of between about 10% to about 20% by weight, or about 10%, 11%, 12%. 13%. 14%, 15%, 16%, 17%. 18%, 19%, or 20% by weight, or any concentration between any of these values. Suitable synergistic additives may further include long chain polysaccharides having a molecular weight of 1,000 to 25,000 kDA, such as xanthan gum, guar gum and the like; and combinations thereof. In various aspects, the long-chain synergistic additives may be present in the composition in an amount of between about 0.001 to 0.05%, or about 0.001%, 0.005%, 0.01%, or 0.05%, or any concentration between any of these values.

[0023] In various aspects, the method may include adding the composition in an amount of about 100 ppm to about 5000 ppm, or about 100, 200, 300, 400. 500, 600, 700, 800, 900. 1000, 1500, 2000, 2500, 3000, 3500, 4000. 4500 and 5000 ppm, or from about 400 ppm to about 3000 ppm, or about 400 to about 800 ppm, or any amount between any of these values.

[0024] In various aspects, the viscosity of the coke slurry solution may be reduced by at least about 30%, or at least about 40%. or at least about 50%, or any amount between any of these values. In various aspects, the viscosity of the coke slurry solution may be reduced to less than about 800 cP, or less than about 650 cP, or between about 600 cP to 650 cP.

[0025] In various aspects of the disclosed technology, coke slurry solutions comprising the compositions of the disclosure are disclosed. In various aspects, the coke slurry solution may include a solid % loading of up to 67% in slurry, or between about 63% to about 67% in slurry', or between about 60% to about 65% in slurry. In various aspects, the coke slurry' solutions may include 80%-95% petroleum coke solid by weight in a particle size distribution range of between about 0.1 mm to about 10 mm. and 4%- 15% coal solid by weight in a particle size distribution range of between about 0.1 mm to about 15 mm.EXAMPLES

[0026] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the disclosed technology7or limit the scope to any particular embodiments.

[0027] Example 1

[0028] Viscosity measurements for different batches of petroleum coke slurry samples with 63% of solid (petroleum coke / coal solid mix) were performed. The compositions of the disclosed technology were dosed at different dosages against different batches of the slurry samples. One set from each batch was left untreated as a blank for performance comparison.

[0029] The viscosity was measured using a viscometer for -325 mL of the blank petroleum coke slurry solutions and -325 mL of the corresponding slurry solutions treated with various compositions of the disclosed technology7, as shown in Tables 1 and 2 below.

[0030] Composition 1 includes lignosulfonate in an amount of 35 to 45% by weight, an alkyl (C4-C-22) sulfosuccinate in an amount of 5 to 10% by weight, a short chain polyol in an amount of 10 to 20% by weight, and water in an amount of 25 to 50% by weight.

[0031] Composition 2 includes lignosulfonate in an amount of 35 to 45% by weight; alky l (C4-C18) aromatic sulfonic acid in an amount of 5 to 10%, a short chain polyol ether in an amount of 10 to 20% by weight, and water in an amount of 25 to 50% by weight.

[0032] The viscosity performance evaluation was done against different batches of petroleum coke slurry7samples collected at different times, though the solid % loading was around 63% in each instance.

[0033] Detailed results are provided in Tables 1 and 2 below:

[0034] Table 1

[0035] Table 2

[0036] Example 2

[0037] Viscosity was measured for a 60-70% solid loaded petroleum coke slurry after individual addition of lignosulfonate, long chain polysaccharides, and ethylene oxide and propylene oxide-based tri-block co-polymers. The results are shown in Table 3 below.

[0038] Table 3should be understood that the present disclosure is not so limited and modifications may be made without departing from the disclosed technology'. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.

Claims

CLAIMS1. A liquid composition for improving the flowability and / or rheology of a coke slurry solution, the liquid composition comprising a lignosulfonate derivative.

2. The liquid composition according to claim 1, wherein the lignosulfonate derivative is selected from sodium, calcium, magnesium, and ammonium salts of lignosulfonate, or combinations thereof.

3. The liquid composition according to claim 1 or 2, wherein the liquid composition further comprises a surfactant.

4. The liquid composition according claim 3, wherein the surfactant comprises an anionic surfactant, a nonionic surfactant, or combinations thereof.

5. The liquid composition according to claim 3 or 4, wherein the surfactant comprises a di-alkyl (C4-C22) sulfosuccinate, alkyl (C-6 to C-18) aromatic sulfonates, or combinations thereof.

6. The liquid composition according to any one of claims 3-5. wherein the surfactant comprises ethylene oxide and propylene oxide-based tri-block co-polymers having a molecular weight of between about 6000 to 15000 daltons, or combinations thereof.

7. The liquid composition according to any one of claims 1-6, wherein the liquid composition further comprises one or more synergistic additives of high or low molecular weight.

8. The liquid composition according to claim 7, wherein the one or more synergistic additives comprises butoxy ethanol, butoxy ethoxy ethanol, propylene glycol, methyl substituted pentane diol, ethylene glycol and combinations thereof.

9. The liquid composition according to claim 7, wherein the one or more synergistic additives comprises a long chain polysaccharide having a molecular weight between about 1000 to 25000 kDa.

10. The liquid composition according to claim 9, wherein the long chain polysaccharide is xanthan gum.

11. A coke slurry solution comprising the liquid composition according to any one of claims 1-10.

12. The coke slurry solution according to claim 11, wherein the coke slurry solution comprises a solid % loading of up to 67% in slurry.

13. A method of reducing the viscosity' of a coke slurry solution comprising adding to the coke slurry solution a liquid composition comprising a lignosulfonate derivative.

14. The method according to claim 13, wherein the lignosulfonate derivative is selected from sodium, calcium, magnesium, and ammonium salts of lignosulfonate, or combinations thereof.

15. The method according to claim 13 or 14, wherein the liquid composition further comprises a surfactant.

16. The method according to claim 15, wherein the surfactant comprises an anionic surfactant, a nonionic surfactant, or combinations thereof.

17. The method according to claim 15, wherein the surfactant comprises a di-alkyl (C4-C22) sulfosuccinate, alkyl (C-6 to C-18) aromatic sulfonates, or combinations thereof.

18. The liquid composition according to any one of claims 15-17, wherein the surfactant is selected from ethylene oxide and propylene oxide-based tri-block co-polymerhaving a molecular weight of between about 6000 to about 15000 daltons, or combinations thereof.

19. The method according to any one of claims 13-18, wherein the liquid composition further comprises one or more synergistic additives of high or low molecular w eight.

20. The method according to claim 19, wherein the one or more synergistic additives comprises butoxy ethanol, butoxy ethoxy ethanol, propylene glycol, methyl substituted pentane diol, ethylene glycol and combinations thereof.

21. The method according to claim 19, wherein the one or more synergistic additives comprises a long chain polysaccharide having a molecular weight between about 1000 to about 25000 kDa.

22. The method according to claim 21, wherein the long chain polysaccharide is xanthan gum.

23. The method according to any one of claims 13-22, wherein the method comprises adding the liquid composition in an amount of about 100 to about 1000 ppm.

24. The method according to claim 23, wherein the method comprises adding the liquid composition in an amount of about 400 to about 800 ppm.

25. The method according to any one of claims 13-24, wherein the viscosity of the coke slurry solution is reduced by at least about 30%.

26. The method according to any one of claims 13-25, wherein the viscosity of the coke slurry solution is reduced to less than about 800 cP.

27. The method according to claim 26, wherein the viscosity’ of the coke slurry solution is reduced to less than about 650 cP.

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