CN115305071B - Phenolic aldehyde system weak gel profile control agent, modifier and preparation method thereof - Google Patents

Phenolic aldehyde system weak gel profile control agent, modifier and preparation method thereof Download PDF

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CN115305071B
CN115305071B CN202110502145.1A CN202110502145A CN115305071B CN 115305071 B CN115305071 B CN 115305071B CN 202110502145 A CN202110502145 A CN 202110502145A CN 115305071 B CN115305071 B CN 115305071B
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acid monoglyceride
organic acid
water
nitrite
regulator
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CN115305071A (en
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时昌新
张明龙
王哲
何萌
陈亚娟
宋御冕
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents

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Abstract

The application provides a regulator for a phenolic aldehyde system weak gel profile control agent, which comprises organic acid monoglyceride, nitrite, an antioxidant and water. Wherein the organic acid monoglyceride comprises a C1-C4 organic acid monoglyceride; preferably, the C1-C4 organic acid monoglyceride comprises one or more of formic acid monoglyceride, acetic acid monoglyceride, propionic acid monoglyceride and isobutyric acid monoglyceride. The regulator of the phenolic aldehyde system weak gel profile control agent has good water solubility, can form uniform and stable solution with the crosslinking agent, can improve the stability of an adhesive system, keeps the viscosity of the crosslinking system, and further improves the profile control effect.

Description

Phenolic aldehyde system weak gel profile control agent, modifier and preparation method thereof
Technical Field
The application relates to the field of petroleum exploration, in particular to a phenolic aldehyde system weak gel profile control agent, a phenolic aldehyde system weak gel profile control regulator and a preparation method of the phenolic aldehyde system weak gel profile control agent.
Background
When the development of the old oil field successively enters a medium-high water-containing period, a plurality of contradictions in the development process are gradually developed. In the water injection development process, the injected water can flow into the production well along the hypertonic layer due to the heterogeneity of the reservoir plane and longitudinal direction and the difference of the viscosity of the oil-water phase, and a superior water flow potential channel is formed in the hypertonic layer, so that water cones, water channeling and the like are formed, the oil well can be exposed to water prematurely or flooded in the early stage of development, and the water content rising speed is obviously accelerated. Meanwhile, the ineffective circulation of injected water is formed, the water flooding efficiency of an oil layer is low, the yield is reduced, the oil extraction speed is reduced, the contradiction is more prominent along with the extension of the development time of an oil field, the stable production of the oil field is severely restricted, and therefore the flooding adjustment of a water injection well is very necessary to be carried out.
The profile control agent adopted in the current indoor research and oilfield mining experiments belongs to a weak gel system, and mainly consists of a polymer and a cross-linking agent. The polymer is mainly polyacrylamide and xanthan gum. The cross-linking agent system used for weak gel mainly comprises: phenolic crosslinking systems, cr (III) crosslinking systems, al (III) metal crosslinking systems, and the like. Metal crosslinking systems are most used in low temperature formations <70 ℃. The composite cross-linking agent is usually composed of a phenolic aldehyde system and a metal system, and is suitable for medium-low temperature oil reservoirs at 70-90 ℃. A multi-purpose phenolic aldehyde cross-linking system for medium-high temp (90 deg.C) oil deposit. Phenolic resin cross-linking agent systems are generally composed of formaldehyde, phenol and polyacrylamide, wherein formaldehyde and phenol can be cross-linked with acrylamide groups of polymers to form gel, formaldehyde and phenol in the system can react to form phenolic resin, and the phenolic resin with active groups can be continuously polycondensed with the amino groups in the polyacrylamide to form gel. In order to perform profile control of a deep stratum, the aim of delaying crosslinking is needed to be fulfilled, and an acrylamide polymer, urotropine, phenol and other systems can be adopted. The basic principle is that urotropine generates formaldehyde under the condition of an acidic medium and/or a high-temperature environment, and then formaldehyde reacts with phenol to generate polyhydroxy phenol, and the polyhydroxy phenol and the formaldehyde can be crosslinked with polyacrylamide to form gel.
The acidic medium commonly used in phenolic systems is oxalic acid or ammonium chloride (Liu Yuli, etc.). In addition, in order to improve the stability of the system, the interference of oxygen in water is often required to be removed, so that an oxygen scavenger needs to be added. A commonly used oxygen scavenger is thiourea. At the same time, urea (Yu Lihong, etc.) is often added in order to improve the properties of the crosslinker system. Thiourea contains amine groups in the molecule, so that ammonia is easily decomposed, ammonium chloride contains ammonia, and urotropine is decomposed to generate ammonia (Chen Saitong and the like). The generation of ammonia not only changes the pH of the gel, but also deteriorates the water solubility of the crosslinking agent (Luo Cuirui, etc.). Therefore, there is a need to find suitable regulators to achieve the cross-linking gelling properties of phenolic systems.
[ Reference ] to
Liu Yuli A low cost HPAM phenolic gel system [ J ]. Applied chemical industry, 2014, 43 (5): 883-886;
Yu Lihong laboratory experiments on HPAM phenolic/urea formaldehyde composite cross-linked polymer gel temporary plugging agent [ J ], fine petrochemical progress, 2014, 15 (5): 17-19];
chen Saitong study of temperature-resistant salt-resistant weak gel profile control system [ D ], university of northeast petroleum, 2016; luo Cuirui Synthesis and modification of Low molecular weight Water-soluble phenolic resin [ D ], university of Harbin, 2010.
Disclosure of Invention
In order to solve the technical problems, the application provides a regulator for a phenolic aldehyde system weak gel profile control agent, which comprises organic acid monoglyceride, nitrite, an antioxidant and water.
According to one embodiment of the invention, the organic acid monoglyceride comprises a C1-C4 organic acid monoglyceride; according to one embodiment of the present invention, the C1-C4 organic acid monoglyceride includes one or more of formic acid monoglyceride, acetic acid monoglyceride, propionic acid monoglyceride, and isobutyric acid monoglyceride.
According to one embodiment of the invention, the nitrite comprises one or more of sodium nitrite, potassium nitrite, or lithium nitrite.
According to one embodiment of the invention, the antioxidant comprises ascorbate, erythorbate, a metal compound, sulfate or sulfite.
According to one embodiment of the invention, the weight ratio of the components comprises 5-20% by weight of C1-C4 organic acid monoglyceride, 5-15% by weight of nitrite, 1-5% by weight of antioxidant and the balance of water.
Another aspect of the present invention is to provide a phenolic system weak gel profile control agent comprising the above-described conditioning agent, the phenolic system weak gel profile control agent comprising a conditioning agent as described above, and a polymer, a phenolic crosslinker, and/or an oxygen scavenger.
According to one embodiment of the invention, the polymer guar gum, xanthan gum, galactomannan gum and derivatives thereof, cellulose and cellulose derivatives thereof, polyacrylamide and partially hydrolyzed polyacrylamide.
According to one embodiment of the invention, the phenolic cross-linking agent comprises an aldehyde compound, a phenol compound or a derivative thereof.
According to one embodiment of the invention, the aldehyde compound comprises formaldehyde, methyl formaldehyde, butyl formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, valeraldehyde, caproaldehyde, heptanal, benzaldehyde; a compound decomposable to an aldehyde; preferably, the aldehyde-decomposable compounds include paraformaldehyde, trioxane, furfural, hexamethylenetriamine, hexamethylenetetramine, alditol, β -hydroxybutyraldehyde and acetals and mixtures thereof.
According to one embodiment of the invention, the phenolic compound comprises one or more of resorcinol, catechol, hydroquinone, pyrogallol, phloroglucinol, dihydroxybisphenol, phenol.
The invention also provides a preparation method of the regulator for the phenolic system weak gel profile control agent, which comprises the steps of mixing water-soluble organic acid monoglyceride, nitrite, an antioxidant and water; preferably, the regulator comprises the following components in parts by weight: 5-20% of C1-C4 organic acid monoglyceride, 5-15% of nitrite, 1-5% of antioxidant and the balance of water.
The inventors found that: the water-soluble monoglyceride is used for hydrolyzing to generate glycerin and organic acid, wherein the organic acid plays a role in promoting formaldehyde generation by decomposing aldehyde compounds such as urotropine, and meanwhile, the generated organic acid can be combined with calcium and magnesium ions in water to avoid influencing the viscosity of polyacrylamide. Secondly, the organic acid generated by using water-soluble monoglyceride and nitrite are used for generating nitrous acid, and the nitrous acid reacts with aldehyde compounds such as urotropine and oxygen scavenger such as ammonia generated by the decomposition of thiourea, so that the cross-linking of ammonia and the aldehyde compounds such as formaldehyde is avoided, and the gel forming performance of the system is influenced. In addition, the added antioxidant, such as sodium ascorbate, can react with oxygen to avoid oxidation of sodium nitrite by oxygen, so as to ensure the stability of the regulator. The present invention has been completed based on this finding.
Compared with the prior art, the invention has at least the following effects: the regulator for the phenolic aldehyde system weak gel profile control agent has good water solubility, can form uniform and stable solution with the crosslinking agent, can improve the stability of an adhesive system, keeps the viscosity of the crosslinking system, and further improves the profile control effect.
Drawings
FIG. 1 is a graph of the effect of a modifier on a phenolic system weak gel system in one embodiment of the invention;
FIG. 2 is a graph of the effect of a modifier on a phenolic system weak gel system in another embodiment of the invention;
FIG. 3 is a graph showing the effect of oxalic acid as a regulator on a weak gel system of a phenolic system under the same conditions.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Applicants have created compositions and related methods for controlling cross-linking of cross-linkable phenolic systems in well treatment fluids using water soluble organic acid monoglycerides, nitrites, antioxidants, and cross-linking agents, and applied such compositions and methods to a number of hydrocarbon recovery operations.
In general, a polymer refers to a natural or synthetic substance composed of a large number of macromolecules of high molecular weight, which are compounded from simple molecules (monomers). In the present invention, the polymers include typical crosslinkable organic polymers, sometimes referred to herein equivalently as "gels" or "weak gels", which may be included in the profile-modifying agents and systems described herein, particularly in aqueous fluids and systems, and may be generally used with the present invention.
The polymers of the present invention comprise biopolymers, synthetic polymers, or combinations thereof, wherein the crosslinkable organic polymers of "weak gels" or "phenolic system weak gels" comprise at least slightly soluble in water (where slightly soluble means having a solubility of at least about 0.01kg/m 3). Without limitation, these crosslinkable organic polymers can be used to increase the viscosity of the system during application. Various polymers may be used in conjunction with the methods and compositions of the present invention, and the polymers may be biopolymers comprising natural, modified and derivatized polysaccharides and derivatives thereof, which comprise one or more monosaccharide units selected from the group consisting of galactose, mannose, glucoside, glucose, xylose, arabinose, fructose, glucuronic acid. Suitable polymers that may be used in accordance with the present disclosure include, but are not limited to, guar gum, hydroxypropyl guar (HPG), cellulose, carboxymethyl cellulose (CMC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxyethyl cellulose (HEC), guar gum, xanthan gum, other derivatives of galactomannan gum; such as various celluloses, e.g., carboxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose; alkyl celluloses such as methyl cellulose, ethyl cellulose, and propyl cellulose; alkyl carboxyalkyl celluloses, such as ethyl carboxymethyl cellulose; alkyl celluloses such as methyl ethyl cellulose; hydroxyalkyl celluloses such as hydroxypropyl methylcellulose; and combinations thereof, and the like. Preferably, according to one non-limiting embodiment of the present disclosure, the polymer is guar gum, hydroxypropyl guar (HPG) or hydroxymethyl cellulose, partially hydrolyzed hydroxymethyl fiber, alone or in combination.
The resin composition in one embodiment of the present invention includes all resins known in the art that are capable of forming a hardened, consolidated mass. Many such resins are commonly used in profile-shifting operations, and in one implementation of the present invention, the resins include two-part epoxy resins, novolac resins, polyepoxide resins, phenolic resins, urea-formaldehyde resins, polyurethane resins, furan/furfuryl alcohol resins, phenolic/latex resins, phenol formaldehyde resins, polyester resins, and mixtures and copolymers thereof, polyurethane resins, and mixtures and copolymers thereof, acrylate resins, and mixtures thereof.
In the present invention, the regulator is preferably a water-soluble glyceride; preferably, in one embodiment of the present invention, the water-soluble glyceride comprises an organic acid monoglyceride; in one embodiment of the invention, the organic acid glyceride comprises a water-soluble organic acid monoglyceride; preferably the water-soluble organic acid monoglyceride comprises a C1-C4 organic acid monoglyceride; more preferably comprises one or more of formic acid monoglyceride, acetic acid monoglyceride, propionic acid monoglyceride, isobutyric acid monoglyceride, and butyric acid monoglyceride.
In the invention, the water-soluble glyceride or the water-soluble organic acid monoglyceride is hydrolyzed in water to generate glycerin and organic acid, wherein the organic acid plays a role in promoting formaldehyde generation by decomposing aldehyde compounds such as urotropine, and meanwhile, the generated organic acid can be combined with calcium and magnesium ions in water to avoid influencing the viscosity of polyacrylamide.
In the present invention, the regulator preferably uses nitrite which can react with organic acid generated by water-soluble monoglyceride to generate nitrous acid which can react with the aldehyde compound such as urotropine and/or oxygen scavenger such as ammonia generated by the decomposition of thiourea to avoid cross-linking of ammonia with the aldehyde compound such as formaldehyde, thereby affecting the gelling performance of the system. In one embodiment of the present invention, the water-soluble organic acid monoglyceride comprises one or more of sodium nitrite, potassium nitrite, or lithium nitrite in one embodiment of the present invention. Preferably, in one embodiment of the present invention, the nitrite includes sodium nitrite, potassium nitrite.
In the present invention, the regulator is preferably added with an antioxidant, which in one embodiment of the present invention includes ascorbate, isoascorbate, metal compound, sulfate or sulfite. The antioxidant added in the invention, such as sodium ascorbate, can react with oxygen, so that sodium nitrite is prevented from being oxidized by the oxygen, and the stability of the regulator is ensured. In one embodiment of the invention, the regulator for the weak gel profile control agent of the phenolic system comprises water-soluble organic acid monoglyceride, nitrite, an antioxidant and water.
Preferably, in one embodiment of the invention, the weight ratio of each component in the regulator for the phenolic system weak gel profile control agent comprises 5-20% by weight of C1-C4 organic acid monoglyceride, 5-15% by weight of nitrite, 1-5% by weight of antioxidant and the balance of water.
In one embodiment of the invention, the aldehyde compounds in the phenolic system comprise formaldehyde, methyl formaldehyde, butyl formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, valeraldehyde, caproaldehyde, heptaldehyde and benzaldehyde; a compound decomposable to an aldehyde; preferably, the aldehyde-decomposable compounds include paraformaldehyde, trioxane, furfural, hexamethylenetriamine, hexamethylenetetramine, alditol, β -hydroxybutyraldehyde and acetals and mixtures thereof.
In one embodiment of the present invention, the phenolic compound in the phenolic system comprises one or more of resorcinol, catechol, hydroquinone, pyrogallol, phloroglucinol, dihydroxybisphenol, phenol.
In one embodiment of the invention, the phenolic system weak gel profile control agent comprises the conditioning agent, and a polymer, a phenolic crosslinking agent, and/or an oxygen scavenger.
Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the examples, while indicating specific embodiments of the invention, are given by way of illustration only. In addition, it is contemplated that alterations and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Description of illustrative embodiments
[ Example 1]
Based on 100 g of the total amount, 10% by weight of formic acid monoglyceride, 10% by weight of sodium nitrite, 2% by weight of sodium erythorbate and the balance of water are added to water, and then formic acid monoglyceride is added and stirred for one hour to obtain the crosslinking agent regulator.
[ Example 2]
Based on 100 g of the total amount, 10% by weight of formic acid monoglyceride, 5% by weight of sodium nitrite, 3% by weight of sodium erythorbate and the balance of water are added to water, and then formic acid monoglyceride is added and stirred for one hour to obtain the crosslinking agent regulator.
Experimental example 1
The following description is made regarding the methods for using the regulators prepared in examples 1 and 2 described above:
experimental water: the water source well water of the salix integra 10 broken block of the oil extraction plant of the North China oilfield. Mineralization degree 522mg/L.
The polymer used was polyacrylamide with a molecular weight of 1900 ten thousand (product number 62523) from Beijing Heng polymerization chemical group Co., ltd. A concentration of 1200mg/L was used.
The cross-linking agent is phenol: the urotropine is prepared from 800mg/L and 8000 mg/L. Purchased from North China oilfield Tiancheng Co.
The regulators prepared in example 1 and example 2 provided in the present invention were added at a concentration of 800mg/L.
For control, ammonium chloride was added as a regulator, using a concentration of 800mg/L (see FIG. 1, as is in FIG. 2).
For control, oxalic acid was added as a modulator, and a concentration of 800mg/L (see modulator corresponding to the broken line in FIG. 3) was used.
And (3) placing the prepared profile control agent solution into a baking oven at 120 ℃ to examine the gelling property. The viscosity was measured using a HAAKE MARS rheometer. The experimental results are shown in fig. 1, fig. 2 and fig. 3.
As shown in fig. 1 and fig. 2, the regulators prepared in example 1 (corresponding to fig. 1) and example 2 (corresponding to fig. 2) are added respectively, so that the stability of the formed cross-linking agent is greatly improved compared with that of the existing regulator (ammonium chloride), and the time of occurrence of the maximum viscosity is later, which is favorable for performing profile control and profile control of the deep stratum.
As shown in FIG. 3, the regulator of the present invention has a higher viscosity-maintaining effect for 25 days or even 30 days under the same use conditions as that of oxalic acid as the regulator (use concentration of 800 mg/L).
All reagents or instruments of the application are commonly used or commercially available. The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (2)

1. The phenolic system weak gel profile control agent is characterized by comprising a regulator, a polymer and a phenolic cross-linking agent;
the regulator comprises organic acid monoglyceride, nitrite, an antioxidant and water; wherein,
The organic acid monoglyceride comprises C1-C4 organic acid monoglyceride; the C1-C4 organic acid monoglyceride comprises one or more of formic acid monoglyceride, acetic acid monoglyceride, propionic acid monoglyceride and isobutyric acid monoglyceride;
The nitrite comprises one or more of sodium nitrite, potassium nitrite or lithium nitrite;
The antioxidant is erythorbate;
The regulator comprises 10% by weight of C1-C4 organic acid monoglyceride, 5% -10% by weight of nitrite, 2% -3% by weight of antioxidant and the balance of water according to the weight percentage;
the polymer comprises one or more of polyacrylamide and partially hydrolyzed polyacrylamide;
the phenolic aldehyde cross-linking agent is prepared from two components of phenol and urotropine according to 800mg/L and 8000mg/L respectively.
2. A method for preparing the regulator for the weak gel profile control agent of a phenolic system according to claim 1, which is characterized in that the regulator is prepared by mixing water-soluble organic acid monoglyceride, nitrite, an antioxidant and water.
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