CN104955919A

CN104955919A - Amide branched aromatic gelling agent enhancers and breakers

Info

Publication number: CN104955919A
Application number: CN201380061361.0A
Authority: CN
Inventors: 肖恩·T·梅谢尔; 奥利维娅·斯图尔德; 丹尼尔·弗思; 罗伯特·莫兰
Original assignee: Synoil Fluids Holdings Inc
Current assignee: Synoil Fluids Holdings Inc
Priority date: 2012-09-24
Filing date: 2013-09-24
Publication date: 2015-09-30

Abstract

A downhole fluid comprises a base fluid, for example a hydrocarbon base fluid, a gelling agent, and a gel enhancer. The gelling agent has an aromatic core of one or more aromatic rings, the gelling agent having two or more amide branches distributed about the aromatic core, each of the two or more amide branches having one or more organic groups. An example gelling agent is a pyromellitamide gelling agent. A method of making a downhole fluid, the method comprising: combining a base fluid, a gelling agent, and a gel enhancer. A downhole fluid comprising a base fluid, a gelling agent, a breaker, and a gel enhancer. Downhole fluids with such gels and a breaker are also disclosed.

Description

The aromatic series jelling agent toughener of acid amides branching and gel breaker

Technical field

The present invention relates to aromatic series jelling agent toughener and the gel breaker of acid amides branching.

Background technology

Benzamide jelling agent has been suggested application or has applied in a lcd display and as acid amides nucleator.Benzene tetramethyl amide gellant has been suggested application or has been applied in organizational project, drug delivery, liquid-crystal display and catalyzer.

Summary of the invention

The invention discloses a kind of down-hole liquid, it jelling agent of aromatic proton comprising base fluid and there is one or more aromatic nucleus, described jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branch has one or more organic group.Gel enhancing agent, gel breaker or both can be added to such liquid.

The invention discloses a kind of down-hole liquid, it comprises base fluid and benzene tetramethyl amide gellant.Benzene tetramethyl amide gellant can have following general formula:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈in be eachly respectively hydrogen or organic group.

The invention also discloses a kind of down-hole liquid, it comprises base fluid, jelling agent and gel enhancing agent, wherein jelling agent has the aromatic proton of one or more aromatic nucleus, described jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branch has one or more organic group.

The invention discloses a kind of method, described method comprises and being incorporated in down-hole formation by down-hole liquid.The invention also discloses a kind of method preparing down-hole liquid, described method comprises: mixed mutually with jelling agent by base fluid.The invention also discloses a kind of composition for gelling down-hole liquid, described composition comprises aromatic series jelling agent and the wetting agent of acid amides branching.

The invention also discloses a kind of jelling agent for down-hole liquid, described jelling agent has following general formula:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈in be eachly respectively hydrogen or C7-24 alkyl group.

The invention also discloses a kind of method, comprise and down-hole liquid be used as wellbore fluid or be used as down-the hole treatment liquid.

The invention discloses a kind of method by down-hole liquid being prepared by the mixing of base fluid, jelling agent and gel enhancing agent.

The invention also discloses a kind of down-hole liquid, it comprises base fluid, jelling agent and gel breaker, wherein jelling agent has the aromatic proton of one or more aromatic nucleus, described jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branch has one or more organic group.

The invention also discloses a kind of down-hole liquid, it comprises base fluid, benzene tetramethyl amide gellant, gel breaker and gel enhancing agent.

In various embodiments, any one or more in following characteristics can be comprised: each acid amides branch is connected to aromatic proton via carbon-to-carbon or carbon-nitrogen bond.One or more acid amides branch is connected to aromatic proton via carbon-nitrogen bond.Each acid amides branch is connected to aromatic proton via carbon-nitrogen bond.There are three or four acid amides branches.Each organic group is alkyl group.Each alkyl group is linear alkyl groups.Each alkyl group has 6-24 carbon atom.Aromatic proton is phenyl ring.Each acid amides branch is connected to aromatic proton via carbon-nitrogen bond, and each organic group is the alkyl group with 6-24 carbon atom.One or more acid amides branch is connected to aromatic proton via C-C, and one or more acid amides branch is connected to aromatic proton via carbon-nitrogen bond.Each alkyl group has 6-12 carbon atom.Aromatic proton is naphthalene nucleus.Each acid amides branch has an organic group.Benzene tetramethyl amide gellant got rid of by jelling agent.Described jelling agent is benzene tetramethyl amide gellant glue.Benzene tetramethyl amide gellant has following general formula:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈in be eachly respectively hydrogen or organic group.R ₅, R ₆, R ₇and R ₈in be eachly respectively hydrogen, and one or more R ₁, R ₂, R ₃and R ₄in each be alkyl group.R ₁, R ₂, R ₃and R ₄in be eachly respectively alkyl group.R ₁＝R ₂＝R ₃＝R ₄。R ₁, R ₂, R ₃and R ₄in each there are at least 6 carbon atoms.Each alkyl group has 6-24 carbon atom.Each alkyl group has 6-10 carbon atom.Each alkyl group is one or more straight chain group, branched group, aromatic group or cyclic group.Each alkyl group is straight chain group.R ₅, R ₆, R ₇and R ₈in each be hydrogen respectively, and R ₁, R ₂, R ₃and R ₄in each be the linear alkyl groups with 6-10 carbon atom respectively.R ₁, R ₂, R ₃and R ₄there are 6 carbon atoms.Base fluid comprises hydrocarbon compound.Hydrocarbon compound has 3-8 carbon atom.Hydrocarbon compound has 3-24 carbon atom.Hydrocarbon compound comprises liquefied petroleum gas (LPG).Base fluid comprise in nitrogen or carbonic acid gas one or more.Also use or be provided with gel breaker.Described gel breaker is that water activates gel breaker, and down-hole liquid comprises hydrate.Gel breaker comprises ion salt further.Described ion salt comprises one or more bromide, muriate, organic salt and amine salt further.Described gel breaker comprises one or more ethanol or alkoxide.One or more described ethanol or alkoxide have 2 or multiple carbon atom.Be provided with alkoxide and alkoxide comprises aluminum isopropylate.Be provided with alkoxide and down-hole liquid comprises hydrate.Gel breaker comprises piperidinium salt and down-hole liquid comprises hydrate.Gel breaker comprises coating layer further.Described coating layer comprises wax further.Gel enhancing agent can be linking agent.Gel enhancing agent comprises organic molecule, such as heterocycle, and it has at least two heteroatomss being spaced apart from each other and having one or more pairs of lone-pair electron separately.Heterocycle forms the ring of 6 atoms, its have be positioned at 1 and 4 places or be positioned at start from 1 and 4 corresponding functional group on two non-carbon.Heterocycle comprises piperazine.Gel enhancing agent comprises metallic compound, potassium tert.-butoxide, diethanolamine, MENTHOL, lactic acid, amygdalic acid, ammonium acetate, paraformaldehyde, Resorcinol, and one or more in tetramethylammonium hydroxide.Be provided with metallic compound and it comprises one or more iron and aluminium.Down-hole liquid has the tensio-active agent for being distributed to by gel enhancing agent in base fluid.Described metallic compound comprises iron (III) vitriol.Gel enhancing agent in tensio-active agent and base fluid forms complex compound.Metallic compound can be dissolved in base fluid by neat form.Described metallic compound comprises metal alkoxide.Described metal alkoxide comprises aluminum isopropylate.Gel enhancing agent comprises aromatic carboxylic acid salt.Aromatic carboxylic acid salt comprises ibuprofen salt.Gel enhancing agent comprises ammonium chloride, trimeric cyanamide, choline chloride 60, and one or more in hexa-methylene diamino chlorine.Jelling agent forms hydrogen bond structure by the intermolecular hydrogen bonding between the acid amides branch of adjacent gellant molecules, and wherein gel enhancing agent is crosslinked or promote intermolecular hydrogen bonding by intermolecular hydrogen bonding.Down-hole liquid has the properties-correcting agent being chosen to gel enhancing agent is transformed into gel breaker.Be provided with the gel enhancing agent lower than threshold concentration, if higher than this threshold concentration, then gel enhancing agent just becomes gel breaker, and wherein said properties-correcting agent comprises the additional source being enough to the concentration of gel enhancing agent is elevated to the gel enhancing agent higher than threshold concentration.Gel enhancing agent comprises piperidines or piperazine.Gel enhancing agent comprises piperidines and properties-correcting agent comprises benzylamine.Gel enhancing agent comprises aromatic carboxylic acid salt, and wherein said properties-correcting agent comprises proton source or cation complexing agents.Proton source comprises acid.Cation complexing agents comprises citric acid, and aromatic carboxylic acid salt comprises ibuprofen salt.Described properties-correcting agent also comprises coating layer.Be provided with gel breaker and gel enhancing agent and different from each other.Gel breaker comprises aromatic carboxylic acid.Gel breaker comprise in Ibuprofen BP/EP and phenylpropionic acid one or more.Gel breaker comprise in diphenyl acetic acid, phenylformic acid and toluylic acid one or more.Be provided with cation complexing agents, wherein aromatic carboxylic acid is salt.Aromatic carboxylic acid comprises ibuprofen salt, and cation complexing agents comprises citric acid.Jelling agent forms hydrogen bond structure by the intermolecular hydrogen bonding between the acid amides branch of adjacent gellant molecules, and hydrogen bond between gel breaker saboteur wherein.Described gel breaker is the hydrogen bonding agent forming hydrogen bond with the acid amides branch of jelling agent, described hydrogen bond than adjacent gellant molecules acid amides branch between intermolecular hydrogen bonding stronger.Down-hole liquid is suitable for use as wellbore fluid.Down-hole liquid is suitable for use as down-the hole treatment liquid.Down-hole liquid is incorporated in down-hole formation.Fractured well sub-surface.Down-hole liquid is reclaimed from down-hole formation, and by reclaimed down-hole liquid cycling and reutilization.Cycling and reutilization also comprises to be removed gel breaker from reclaimed down-hole liquid.Carrier is added with in jelling agent.Described carrier comprises ethylene glycol.Also wetting agent is added with in described jelling agent.Also suspending agent is added with in described jelling agent.In lid, mixing was completed before being incorporated in down-hole formation by down-hole liquid.

These or other side by referring to the device be incorporated to herein and method propose in the claims.

Accompanying drawing explanation

Hereinafter with reference to accompanying drawing, embodiment is described; In the accompanying drawings, identical Reference numeral refers to identical element.In the accompanying drawings:

Fig. 1 illustrates that hydrogen bond is formed;

Figure 1A illustrates the basic structure of the aromatic series jelling agent of acid amides branching;

Figure 1B illustrates the left side and the right side acid amides branch that are connected to aromatic proton respectively via carbon-nitrogen bond and C-C;

Fig. 2 illustrates the solvation presented between alkyl solvents and the benzene tetramethyl amide gellant with linear alkyl groups;

Table 1: the characteristic of the viscosity test of disclosed jelling agent.Viscosity test is measured by Brookfield viscometer (Brookfield viscometer).TB, TH, TO and TD refer to N respectively, N ', N ", N " '-tetrabutyl phenyl-1,2,4,5-tetra-methane amide (TB), N, N ', N "; N " '-four hexyl phenyl-1,2,4,5-tetra-methane amides (TH), N, N ', N ", N " '-four octyl phenyls-1,2,4,5-tetra-methane amide (TO) and N, N ', N "; N " '-four decyl phenyl-1,2,4,5-tetra-methane amides (TD);

Figure 40 is the graphic representation of the data of Figure 39, and the viscosity under different shear rate is shown;

Figure 41 is the graphic representation of Figure 39 shearing rate and shear-stress, shows non-newtonian feature;

Figure 42 is the viscosity of TB in hexanaphthene and the graphic representation of concentration;

Figure 43 is the structural representation of various benzene tetramethyl amide rotomers;

Figure 44 is TH's ¹h NMR spectrogram;

Figure 45 is TH's ¹³c NMR spectrogram;

Figure 46 is TO's ¹h NMR spectrogram;

Figure 47 and Figure 48 is TO's ¹³cNMR spectrogram; Wherein, Figure 48 is the demi-inflation (expansion) of spectrum in Figure 47 that alkyl peak value is shown;

Figure 49 is TO in Figure 46 ¹the expansion of H NMR spectrogram;

Figure 50 is respectively under the differing temps of 25 DEG C, 30 DEG C, 50 DEG C and 70 DEG C TH's from bottom spectrum to top spectrum ¹h NMR spectrogram;

Figure 51 is respectively under the differing temps of 25 DEG C, 30 DEG C, 50 DEG C and 70 DEG C TO's from bottom spectrum to top spectrum ¹h NMR spectrogram;

Figure 52 is that the acylamino hydrogen of TO changes temperature variant graphic representation;

Figure 53 is that the acylamino hydrogen of TH changes temperature variant graphic representation;

Figure 54 is for adding the different graphic representation measuring the viscosity that ethylene glycol obtains in TG740 fracturing liquid; Ethylene glycol solution has Dynol by 0.87g tetra-hexyl benzene four methane amide (TH) ^tMformed in the 100mL ethylene glycol of 604 tensio-active agents (the TH concentration of 15mM).

The viscosity that Figure 55 is 5mM TH gelling mixture in TG740 after the four butyl bromation amine adding neat form respectively and the Tetrabutyl amonium bromide being coated with wax form (in wax form) and the graphic representation of time;

The viscosity that Figure 56 is 5mM TH gelling mixture in SD810 after the four butyl bromation amine adding neat form respectively and the four butyl bromation amine being coated with wax form and the graphic representation of time;

Figure 57 is the N of the 10mM in SF840, N ', N "-three hexyls, N " ' viscosity of-benzyl phenyl-1,2,4,5-tetra-methane amide and the graphic representation of temperature and time;

Figure 58 is that the TH of 15mM in the SF840 with Dynol 604 is at the viscosity be placed after the iron gel enhancing agent then adding different amount whole night and the graphic representation of time;

Figure 59 is SF840 and by TH (concentration of 10mM), Dynol 604, the mixture of 10 milliliters of compositions of ethylene glycol and Trometamol to the full extent from the viscosity of iron gel enhancing agent blending of different amounts and the graphic representation of time that add base fluid to;

Figure 60 is SF840 and by TH (concentration of 10mM), Dynol 604, the mixture of 5 milliliters of compositions of ethylene glycol and Trometamol to the full extent from viscosity and the graphic representation of time of the iron gel enhancing agent blending of added different amounts;

Figure 61 is viscosity and the graphic representation of time of various TBuA derivative gel breaker;

Figure 62 is the three-dimensional side view preparing the system and method for down-hole liquid and the method for application down-hole liquid;

Figure 63 is the three-dimensional side view of the drill bit of drilling well;

Figure 64 is the graphic representation of the viscosity of four acid amides that various 1,2,4,5-replaces.

Embodiment

The improvement of unsubstantiality can be carried out to embodiment as herein described when not deviating from the scope that claim contains.

With reference to Figure 1A-B, disclose the aromatics into the acid amides branching as the useful jelling agent of down-hole liquid in the present invention.Jelling agent is a kind of reagent of thickening liquid.This jelling agent has the aromatic proton of one or more aromatic nucleus as shown in Figure 1A.The acid amides branch of two or more (such as three to six or more) distributes around aromatic proton, and each of two or more acid amides branch has one or more organic group.Each acid amides branch can be connected to aromatic proton via carbon-to-carbon or carbon-nitrogen bond as shown in fig. 1b.

An example of the aromatic series jelling agent of acid amides branching is benzene four methane amide.Benzene four methane amide has basic structure general formula (1) as follows:

The invention discloses a kind of benzene four methane amide of the useful jelling agent as down-hole liquid.Such as, a kind of applicable jelling agent has following general formula:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈be eachly respectively hydrogen or organic group.The organic group discussed for all embodiments disclosed is in the present invention applicable to below for the description of different organic group.R ₅, R ₆, R ₇and R ₈each can be hydrogen (example of non-organic group), and R ₁, R ₂, R ₃and R ₄in one or more or all can be respectively alkyl group (example of organic group).In some cases, R ₁=R ₂=R ₃=R ₄.R ₁, R ₂, R ₃and R ₄eachly can have at least 6 carbon atoms respectively, such as 6-10 or 6-24 carbon atom.Each alkyl group is one or more straight chain group, branched group, aromatic group or cyclic group.But preferably, each alkyl group is straight chain group; Such as, if R ₅, R ₆, R ₇and R ₈each be hydrogen, then R ₁, R ₂, R ₃and R ₄in the alkyl group of each straight chain for having 6-10 carbon atom.In one embodiment, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈be eachly respectively hydrogen or C7-24 alkyl group.Organic group can comprise functional group, such as ester class.Except following benzene four methane amide synthesized and test, to synthesize and the example being successfully applied to benzene four methane amide of gel TG740 comprises R ₅, R ₆, R ₇and R ₈be eachly respectively hydrogen and R ₁=R ₂=R ₃=R ₄mixture; Wherein, R ₁be equivalent to n-amyl group (being selected from the 1-amylamine used in acid amides synthesis), R ₁=CH (Me) CH2CH3 (being selected from the 2-aminobutane used in acid amides synthesis), R ₁=CH (Me) CH2CH2CH2CH2CH3 (being selected from the 2-aminoheptane used in acid amides synthesis), R ₁=CH (Me) CH2CH2CHMe2 (being selected from amino-5 methyl hexanes of the 2-used in acid amides synthesis), R ₁=CH2CH (Et) CH2CH2CH2CH3 (being selected from the 2-ethylamino hexane used in acid amides synthesis).Tested also have four cyclohexyl, four phenmethyls, tetraallyl, four n-butyl and four t-butylbenzene four methane amides.

The down-hole liquid (such as down-the hole treatment liquid) comprising jelling agent can comprise base fluid, such as with the hydrocarbon compound base fluid of 3-8 carbon atom, further such as liquefied petroleum gas (LPG).In other embodiments, the hydrocarbon compound base fluid of C3-24 can also be used.In certain embodiments, jelling agent and down-hole liquid do not comprise phosphorus.The basic structure of the aromatic series jelling agent of acid amides branching disclosed herein thinks the major cause of its gelling mechanism, and its change on side chain contributes to the customization (tailor) of synthesized gel rubber.The successful test reported herein and performance that is open and that report herein and mechanism support the aromatic series of acid amides branching with other non-test base fluid (such as nonpolar base fluid and hydrocarbon compound base fluid) and the use of benzene four formaldehyde gel.Based on predicting disclosed for certain but untested entity has the correlated performance identical with corresponding test entity, therefore be predicted as certain for this kind of entity and there is practicality, described entity comprises gel, gel promotor, gel breaker, liquid, and other compound reported herein.

Down-hole liquid also can comprise suitable gel breaker, such as ion salt, such as, comprise one or more in bromide, muriate, organic salt and amine salt, such as quaternary amine (quaternary amine salt).The synergy (1 equivalent (equivalent)) (such as muriate > acetate > bromide > nitrate) of little negatively charged ion can by reducing the 2-3 times of order of magnitude and then induced gel changes solution into by viscosity.The dissociation time of gel and the bonding strength of negatively charged ion proportional.

Gel breaker can comprise in ethanol or alkoxide one or more, such as there is 2 or multiple carbon atom, such as propyl alcohol.Alkoxide can comprise aluminum isopropylate.In some cases, gel breaker may need water source to activate gel breaker and then to destroy gel; Such as, if use the solid alkoxide as aluminum isopropylate.The water source used may be come from the primitive water in stratum (formation).In some cases, hydrate or other can the compound of slow releasing water can be certain retardation rate used by the down-hole liquid being such as embedded in injection.Such as, hydrate disclosed in the Canadian Patent that can be used in No.2685298, and this hydrate comprises the hydration gel breaker (hydrated breaker) of the crystalline structure containing water, wherein water to be strapped in crystalline structure and can be released in fracturing liquid.Such as, the hydrate of any one in magnesium chloride, sodium sulfate, bariumchloride, calcium chloride, magnesium sulfate, zinc sulfate, calcium sulfate and Tai-Ace S 150 can be used.NaSO can be used ₄-10H ₂o is as an example of sodium sulfate hydrate.Ion salt hydrate or covalency hydrate can be used.Can be used in combination with the crystal water added by gel breaker coating layer or packing (encapsulation).

Another example that water can activate gel breaker is piperidinium salt.Unlike piperazine, the gel breaker with an amine can destroy the hydrogen bond structure of the gelling being considered to responsible gel.Piperidines is a kind of effective gel breaker, but piperidines is liquid; Therefore, not necessarily practicality in gel breaker is used as extensive.Therefore piperidines hydrogen chloride salt, piperidine hydrochloride salt carry out synthesizing and testing as solid-state gel breaker.Once piperidine hydrochloride is added in the TH of the 100ml of TG740 gelling soln, its viscosity does not have a greater change.Add a small amount of water (20), although make two-layer liquid seem not miscible a little because there are some bubbles, the viscosity of solution obviously reduces.

Canonical process for the synthesis of piperidinium salt (being hydrogenchloride piperidines in this case) is as follows.Being cooled to before 0 DEG C with ice bath, in round-bottomed flask, add aqueous hydrochloric acid (2M, 58.5mL).Dropwise add piperidines (10.0g, 117mmol, 11.6mL) more than 30 minutes, simultaneously to solution vigorous stirring.Once all piperidines add, then remove desolventizing with ethanol, and recrystallize goes out yellow solid in ethanol, filter, by cold washing with alcohol, to obtain required white solid piperidine hydrochloride.Productive rate (yield) is 0.95g, 7.82mmol, 6.7%, and fusing point: 245 DEG C (actual fusing point: 246-247 DEG C).

Added in gel by following gel breaker and test, display viscosity significantly declines, this gel breaker comprises: be greater than the DODECANOL, 1-of 98%, the TEBA of 99%, the 4-butyl ammonium hydrogen sulfate of 99%, the toluenesulfonic acid sodium salt of 95%, the ferrous sulfate (III) of 97%, the 2-chloro-N-N-diethyl ethanamine hydrogenchloride amine of 99%, the mercaptodiacetic acid of 98%, the pyruvic acid of 98%, the 2-hydroxyl benzylalcohol of 99%, the nonane diacid of 98%, the pentanedioic acid of 99%, the propanedioic acid of 99%, the 1-octylame of 99%, the hexahydroaniline of 99%, the L-AA of 99%, the ethanamide of 99%, molecular weight is the polyvalent alcohol (vinyl alcohol) of 99% of 89000-98000, the quadrol of 99.5%, the Beta-alanine of 99%, the L-PROLINE of 99%.

Following gel breaker is added in gel and tests, display viscosity slightly reduces, this gel breaker comprises: be greater than the benzyl tributyl ammonia chloride of 98%, the anhydrous T-butanols of 99.5%, 2-ethyl-the n-butyl alcohol of 98%, 2-ethyl-1-the hexanol of 99.6%, the 1-hexanol of 99%, the n-butyl alcohol of 99.8%, the 2-aminobutane of 99%, 2-ethyl-1-the hexylamine of 98%, the benzylamine of 99%, the piperidines of 99%, the Virahol of 99.7%, in methyl alcohol, weight percent is the benzyl trimethyl oxyammonia of 40%, and volume percent is the four-n-butyl oxyammonias of 40% in water.

Gel breaker can be configured to delayed fracture effect.Such as, by carrying out coated to gel breaker, time lag gel breaker can be obtained; The coated of this gel breaker such as selects a kind of passing along with the down-hole time with the material of predetermined speed release gel breaker, such as wax.With reference to Figure 55-56, graphic representation shows when the coated gel breaker of employing wax, and destruction postpones; In this case, this gel breaker is that (neat form, see the line 42 in figure and line 46 for Tetrabutyl amonium bromide; And be coated with wax see the line 40 in figure and line 44).In TG740 and SD810, all prepare the TH solution of 5mM, the Tetrabutyl amonium bromide (0.8g) of molar equivalent or the Tetrabutyl amonium bromide (1.0g) that is coated with wax are added in solution.Moral of spending money is strangled viscometer (chandler viscometer) and is examined viscosimetric change.TG740 shows as the TH mixture result of solvent, and the initial viscosity being enclosed with the gel breaker of wax is 93.6cPa, and the initial viscosity not wrapping up the gel breaker of wax is 68.3cPa.And SD810 shows as the result of the TH mixture of solvent, the initial viscosity being enclosed with the gel breaker of wax is 97.7cPa, and the initial viscosity not wrapping up the gel breaker of wax is 100.3cPa.Wherein there is notable difference as between the gel breaker being enclosed with wax of solvent and sterling gel breaker in TG740; Although SD810 finds out to have delayed action as the gel breaker being enclosed with wax of solvent, the difference between itself and sterling gel breaker is also not obvious.Compared with sterling gel breaker, the viscosity drop low rate being enclosed with the gel breaker of wax acting on SD810 solvent is slower.But with TG740 solvent phase ratio, degraded (degradation) speed of the gel breaker of the coated wax in SD810 solvent and the gel breaker of not coated wax is all slower.

Visual assay is carried out as gel breaker, and not show viscosity after in gel and to reduce or the compound that show viscosity increase in some cases comprises being added to: 99% 1, 3-dihydroxy-benzene (Resorcinol), the diphenyl acetic acid of 99%, the imidazoles of 99%, the propionic acid amide of 97%, magnesiumcarbonate, the citric acid of 99.5%, the phenylformic acid of 99.5%, the toluylic acid of 99%, the phthalimide potassium of 98%, the tetramethylolmethane of 99%, the 1-butylamine of 99.5%, the 1-hexylamine of 99%, the hydrogenchloride azanol of 98%, the thanomin of 98%, the L-Histidine of 99%, the Aspartic Acid of 98%, the glycine of 99%, the D-glucitol of 98%.These and other compound can be used as gel enhancing agent or thickening material except jelling agent.

Visual assay is carried out as gel breaker, and the compound that display viscosity increases after being added in gel comprises: the potassium tert.-butoxide of 95%, the piperazine of 99%, 98% diethanolamine, the MENTHOL of 99%, lactic acid, the amygdalic acid of 99%, ammonium acetate, the paraformaldehyde of 95%, the quinhydrones of 99% of 98% of 85%, and volume percent is the Tetramethylammonium hydroxide of 25% in water.These and other compound can be used as gel enhancing agent except jelling agent.

Table 0 below illustrates the further test carried out in possible gel breaker.Use the TH of 10mM in TG740 (42 milliliters) with 100 seconds ^-1shearing rate and standard pressure under carry out the test of 30 minutes.Benchmark viscosity is calculated as: peak viscosity (21 DEG C)=327.41 centipoises (cP), MV minium viscosity (50 DEG C)=154.69 centipoises.

Table 0: the viscosity test result on possible gel breaker.

See Figure 61, the contrast between the gel breaker showing various TBuA derivative.See Reference numeral 48,50,52,54 and 56, refer to the viscosity profile over time after the gelling mixture destruction adopting TH and TG740 to be formed by tetrabutyl disulphide, tetrabutyl nitrate, tetrabutyl phosphonium bromide thing, tetrabutyl hydroborate and tetrabutylammonium acetate salt pair respectively.The not broken glue effect of tetrabutyl disulphide display, and tetrabutyl nitrate at least demonstrates the broken glue characteristic of delay, rear three tetrabutyl derivatives demonstrate broken glue effect fast.In certain embodiments, the non-halogenated gel breaker of less toxicity can be used to replace halo gel breaker.

As described in herein other place, jelling agent by adjacent gellant molecules acid amides branch between intermolecular hydrogen bonding form hydrogen bond structure, and gel breaker can hydrogen bond between saboteur.Suitable gel breaker can comprise the hydrogen bonding agent forming hydrogen bond with the acid amides branch of jelling agent, described hydrogen bond than adjacent gellant molecules acid amides branch between intermolecular hydrogen bonding stronger.Aromatic carboxylic acid gel breaker is considered to operate by this way.Expect protonated COOH group relative to the deprotonation COO-group as gel enhancing agent discussed below and have in hydrocarbon phase the solubleness of raising.The intensity of the hydrogen bond formed by COOH group cause COOH group preferably with hydrogen bonding to gel and other COOH molecule, thus destroy gel network under the concentration exceeding threshold concentration.If the cation complexing agents of such as citric acid uses in conjunction with aromatic carboxylic acid salt, COO-group has the solubleness of raising in hydrocarbon phase, and may cause brokenly glue and for example, see table 0 is about the effect of ibuprofen salt and citric acid example.

Some gel breakers also can be used as gel enhancing agent, as discussed further below.

Down-hole liquid disclosed herein can enter in other compound be applicable to or reagent (such as propping agent) in fusion.Down-the hole treatment liquid disclosed herein can be applicable in the treatment process of down-hole formation, such as fracture treatment as shown in Figure 62.Jelling agent can use in recovery of oil enhancement techniques.

With reference to Figure 62, annexation and other relevant equipment can be omitted although illustrate for the sake of simplicity, in figure, still show a kind of method and system.Base fluid (such as oil gas fracturing liquid) is loaded in storage bucket 10, and pipeline 12 can be flowed through enter in well body 22, be then incorporated in down-hole formation 24, such as oil-bearing formation or gas-bearing formation.Gel can mix with base fluid and prepare down-hole liquid.Such as, in gel storage tank 14, gel can be added to lid (fly), or Gel Pre can be mixed, further such as in storage bucket 10 and base fluid pre-mixing.Also other method can be used to carry out gelling to base fluid.Such as, batch mixing can be utilized to prepare gel.Other storage tank 16 and 18 can be used as required other component (such as propping agent or gel breaker) to be joined respectively in down-hole liquid.

Carrier can be added, such as inert support, as ethylene glycol (ethene glycol) in jelling agent.With reference to Figure 54, being mixed in TG740 by the ethylene glycol solution of the difference amount of the TH by having 15mM, obtaining the graphic representation of corresponding viscosity.After solution is mixed 30 seconds with TG740 fracturing liquid, gel just begins to take shape.Along with the increase of glycol concentration, the viscosity of final mixture is also along with increase.Gel is almost formed immediately.Because jelling agent can not make ethylene glycol gelling, therefore ethylene glycol is believed to be suitable for carrier.On the contrary, before mixing with base fluid, carrier provides a kind of medium for being disperseed as lysate or suspended solids by jelling agent.If jelling agent is solid, for the ease of dispersing or dissolving, before mixing with carrier, tackling jelling agent carry out grinding (ground).Once mix with base fluid, carrier will be dissolved in base fluid such as hydrocarbon compound base fluid, promotes that dissolve gelling agents does not disturb pectisation in base fluid.Use carrier that jelling agent can be allowed to store or transport with low viscosity state in the carrier, simultaneously compared with solid jelling agent or complete jelling agent, use carrier that jelling agent can be promoted to dissolve in base fluid faster, and then gelation rate is also faster in base fluid.Also other carrier be can use, acetonitrile or glycerine comprised, such as Trometamol.

In order to promote jelling agent dispersion in the carrier, suspending agent can be added in jelling agent, such as clay.Suspending agent can play viscosifying agent effect, so that by gel suspendible in the carrier.Suspending agent contributes to jelling agent being kept in the carrier dispersed, and delays or stop jelling agent sedimentation in the carrier.Also other suspending agent can be used, such as various polymkeric substance.

Wetting agent can be added, such as tensio-active agent in jelling agent.Such as, in the mixture tested in Figure 54, by Air Products Company (Air Products ^tM) DYNOL that produces ^tM604 tensio-active agents are used as tensio-active agent.DF-46 is ethylene glycol, DYNOL ^tM604 and the mixture of benzene four methane amide.Wetting agent can contribute to the aromatic series of wetting solid-state acid amides branching and the surface of benzene four formaldehyde gel, and then the dissolving dispersion of accelerating solid, improves gelation time.Such as, for hydrocarbon compound base fluid and benzene tetramethyl amide gellant, ethylene glycol, suspending agent and DYNOL ^tMthe time that the mixture that the solution that 604 tensio-active agents are formed carries out mixing reaches viscosity can be 4 minutes, can be 1 minute or 30 seconds further.Also other wetting agent can be used, such as DYNOL ^tM607.

With reference to Figure 62, down-hole liquid reclaims from down-hole formation 24, such as, reclaimed by recovery line 28, then carries out cycling and reutilization, such as, use one or more recirculation unit 26 to circulate.The recirculation stage can comprise removes one or more components in Ethylene recov, such as, removed by gel breaker.Can also utilize distillation such as to remove ethanol or ammonia, and water can be utilized to be separated such as to remove salt.

When R group contains non-alkyl functional group, such as, in the structure (3) with ester functional group illustrated as follows, compared with being alkyl with R group, its aggreation can be suppressed in hydrocarbon compound liquid.This effect is attributable to the fact that ester group can increase compound polarity, and then is reduced in the solubleness in hydrocarbon compound liquid, and ester group can reduce the geometry consistency with the alkyl of the hydrocarbon compound liquid comprising use.

Exemplary synthesis and correlation test

Although can use other path and stage, the synthesis of tetraalkyl benzene four methane amide was undertaken by two stages:

1, phenyl-1,2, the synthesis of 4,5-tetra-carbonyl tetrachloride (4):

2, the synthesis of acid amides:

The illustrative preparative procedure in path 1 is as follows.Phosphorus pentachloride (45g, 0.22mol) and PMA (25g, 0.11mol) are placed in round-bottomed flask and are mixed together.Heat one end of flask to start reaction with hair drier, impel produce liquid POCl ₃.Once reaction starts, use oil bath heating flask, to continue reaction.Once all solid meltings, POCl ₃by product is by distillation (80-95 DEG C) removing, then use Kugelrohr equipment that product is reduced under vacuum state (150-180 DEG C), produce product needed in white solid (22.7838g, 73.0mmol, 66.4%).

The illustrative preparative procedure in path 2 is as follows, does not wherein use pyridine.By the tetrahydrofuran (THF) (15mL done, phenyl-1 185.0mmol), 2,4,5-tetra-carbonyl tetrachloride (2.0g, 6.0mmol) be dropwise added to by triethylamine (3.5mL, 25.0mmol), the hexylamine (3.23g, 31.2mmol) in methylene dichloride (15mL, 235.0mmol) and dry tetrahydrofuran (THF) (15mL, in solution 185.0mmol) formed, vigorous stirring is carried out to this solution simultaneously.After being added dropwise to complete, this reaction can at room temperature stirred overnight, then filters product, uses rotatory evaporator to remove solvent.Next crude product with methanol and acetone are carried out washing and obtain sterling needed in white solid.Productive rate scope from 0.20g, 0.34mmol, 5.7% to 0.49g, 0.82mmol, 13.7%, to 1.26g, 2.11mmol, 35.2%.Make productive rate reach in the typical production of 35.2%, after hexylamine and triethylamine solution are cooled to 0 DEG C, add chloride of acid again.React remain at this cold condition in the whole adition process of chloride of acid and after having added one hour under.By changing reaction conditions, make to form less throw out, these throw outs are considered to any imide of unwanted triethylamine hydrochloride and formation, therefore can find out, low temperature contributes to forming correct product, instead of unnecessary acid imide, be embodied in productive rate (35.2%) thus and improve.

Gelling is tested.In order to detect the sample of preparation, the compound sample preparing to detect being placed in vial, having the solvent of several milliliters in vial, heated sample is until solution is in clarifying or until reaching the boiling point of solvent.After cooling, if can viscosity be detected, then compound can be said and carry out gelling to solvent.

Gelling mechanism.With reference to Fig. 1, according to the interaction of shown structure, propose to realize the aromatic series of acid amides branching and the gelling of benzene four methane amide by hydrogen bond action between the initial molecular between π-π interaction and amine groups.

Table 2 below indicates the result of the gelling test of four kinds of compounds TB, TH, TO and TD.TB, TH, TO and TD refer to structure (1) above, each with four alkyl groups, are respectively butyl, hexyl, octyl group or decyl, with formed N, N ', N "; N " '-tetrabutyl phenyl-1,2,4,5-tetra-methane amide (TB), N, N ', N "; N " '-four hexyl phenyl-1,2,4,5-tetra-methane amide (TH), N, N ', N "; N " '-four octyl phenyls-1,2,4,5-tetra-methane amide (TO) and N, N ', N "; N " '-four decyl phenyls-1,2,4,5-tetra-methane amide (TD).In table 2 and table 3, TG represents the formation of clear gel; TG* represents the formation only adopting and heat the clear gel carried out; I represents undissolvable; S represents soluble; P represents compound gelling, but precipitates in process of cooling subsequently; PG represent only after vibration with liquid solvent partial gelation, have and need to heat the molecular melting degree that could dissolve in a liquid; And X is equivalent to not form gel, because compound can not be dissolved in liquid.

Table 2: the gelling characteristic of all kinds of SOLVENTS

Table 2 shows that TB, TH, TO and TD gelling is nonpolar, aprotic solvent.This result conforms to the principle forming jelling structure because of intermolecular hydrogen bonding effect.

Table 3: at SYNOIL ^tMgelling characteristic in product

When table 3 shows not stir, and the solvent of not all can be polymerized in gel.By consistent viscosity can be obtained to TG740 vibration.SF800 and SF840 is from not exclusively mixing into.

With reference to Fig. 2 and table 4 below, table 2 with the explanation of the gelling test-results in table 3 can be: compared with aromatic solvent chain, and the arrangement between alkylate chain and alkyl solvents chain can be better, because aromatic solvent chain has larger polarity than straight chained alkyl.In addition, spatial disposition also plays a role.

Table 4

Jelling agent can have the aromatic character of enhancing, to improve the solvation with aromatic solvent.With reference to Figure 57, such as, jelling agent is tested and prepares, wherein R ₁, R ₂and R ₃for hexyl alkyl group, R ₅, R ₆, R ₇and R ₈for hydrogen, and R ₄for phenyl group, to increase aromatic character and to improve aromatic viscosity.In the sample tested in Figure 57, its concentration in SF840 is 10mM, and display has pectisation.

Solvent temperature is tested

With reference to Fig. 3-5 and table 5 below, show TH, TO and TD viscosity test result in TG740 of 10mM concentration.Test-results shows the solubleness of the chain length=increase increased, and because compound polarity diminishes, and causes viscosity to reduce because HYDROGEN BOND INTENSITY dies down.The viscosity be at room temperature almost enhanced instantaneously.Successfully test is not in relevant figure and table for other, and this test comprises and being at room temperature injected in the TG740 of the non-gelling in agitator by the TH gelling sample at TG740 middle and high concentration.

Table 5

Gel type	Peak viscosity (cp)	Time (mins)	Minimum gelation temperature (DEG C)
				TH	707	85	40
TO	421	50	29
				TD	256	40	26

Show as above-mentioned, TB can not gelling TG740.Although TB is dissolvable in water in hexanaphthene, but find, TB can not dissolve in TG740.When being injected in TG740 by the hexanaphthene with TB gelling, define vaporific dispersion state, and there is not gelling in TG740.

Fig. 3-30 illustrates the test-results of the viscosity of TB, TH, TO and TD, as shown in upper table 1.Many results, such as, the result of the TH gelling TG740 shown in Figure 13-15, show that increasing temperature can strengthen viscosity, this is unhoped-for.

With reference to Figure 31-35 and table 6, the various mixtures of jelling agent are tested.These mixtures demonstrate thermal reversion gelling, and this causes the theory of gelling consistent with intermolecular reversible hydrogen bond action.The result of mixture shows that pectisation is that temperature dependency and chain length are dependent.

Table 6

	THTO	THTD	TOTD
				Peak viscosity (cp)	21	15	12
Minimal viscosity (cp)	13	6	5

Table 7-10 below respectively illustrates the viscosity test result of TB, TH, TO and TD.

The viscosity test result of table 7:TB in hexanaphthene

The viscosity test result of table 8:TH in TG740

The viscosity test result of table 9:TO in TG740

The viscosity test result of table 10:TD in TG740

Figure 36-41 shows the shearing test result of TB in hexanaphthene.Figure 36-39 show result show formed gel can shear stablize, as test shown by along with time lapse, shearing rate is constant.Figure 39-41 measures the viscosity of TB in hexanaphthene under different shearing rates, and illustrates between shearing rate and shear-stress to be nonlinear relationship, is indicated as non-newtonian feature thus.

With reference to Figure 42, as shown in the figure, the measurement result of the pectisation of different TB concentration in hexanaphthene is shown to be nonlinear relationship between viscosity and concentration.This result supports that the formation of gelling is theoretical, namely thinks that the formation of gelling forms 3D reticulated structure by the layering self-assembly (hierarchical self-assmbly) of column heap, hurricane band and similar polymer (similar aggregate) to occur.

NMR (Nuclear Magnetic Resonance) spectrum (NMR)

As known in the art, NMR is for measuring molecular structure, and it is based on from high-spin state to the radio-frequency transmissions of low spin states.NMR provide atom environmental form, based on the information such as the quantity (entirety) of proton and the symmetry of molecule in the adjacent ambient of cracking pattern (splitting pattern), environment.Be assumed to be symmetrical molecule, the environment of corresponding proton and carbon is contemplated to be identical.Therefore, in benzene four methane amide of symmetry, NMR data are 1 peak of desired display amide proton and 1 peak of aromatic protons thus.

With reference to Figure 44-51 and table 11, show the NMR data of H and C of TH and TO.

Table 11:NMR peak data

NMR data seem to show that analyzed benzene four methane amide is asymmetry.Such as, ¹the environment showing the proton on phenyl ring in H NMR is different, seems to show that benzene four methane amide is chiral molecular.See ¹h data, seems display 1 amide proton in unique environment clearly, as triplet prove; And as overlapping triplet prove, other 3 amide protons are in similar environment.Figure 43 shows the possible example of rotational isomer, and this example may cause such pattern.Molecule in Figure 43 shows to be from left to right (syn-syn)-(anti-anti), (syn-syn)-(syn-anti), and the example of (syn-syn)-(anti-anti).

Figure 50-51 illustrates under differing temps (VT) ¹h NMR spectrum.VT ¹the NMR spectra of H H key bonding action, also demonstrate that the change of rotational isomer, this change regards that the shape at acid amides H peak raises with temperature and changes as, indicates the change of environment, and the data consistent shown with Figure 16 thus.See Figure 50, TH ¹the VT of the NMR of H shows the rising along with temperature, and chemical shift gradually reduces.In addition, Figure 50 also show the rising along with temperature, and the reduction of the intensity of H key bonding, this is consistent with the data that Figure 16 shows.See Figure 51, TO ¹the VT of H NMR shows upfield shift, and it is described as negative temperature coefficient as usual.In hydrogen-bonded amide group, carbonyl functional group causes amide proton to be moved to downfield.The interatomic mean distance of the thermal fluctuation amount=increase of the temperature=increase raised.Therefore, hydrogen bonding weakens, and amide proton to lesser extent (relative to upfield shift) be moved to downfield.

The temperature dependency of similar acylamino hydrogen displacement is all demonstrated with reference to Figure 52-53, TH and TO.

The disclosed embodiments are provided with low viscous gel or full-bodied gel.An example of low viscosity (2-50cp) gel is SLICK OIL ^tMdesign application, for fine and close formula oil-containing and gas-bearing formation.High-viscosity gel needs additionally to add gel breaker.

The basal component of TG740, SF800 and SF840 is paraffinic hydrocarbons, isoalkane and aromatic hydrocarbons.TG740, SF800 and SF840 are fracturing liquid, and the title that it can be identical or different is bought and obtained in multiple refineries of North America.SD810 or SynDril810 is wellbore fluid, and title that equally can be identical or different is bought and obtained in multiple refineries of North America.

Down-hole liquid disclosed herein can be used as down-the hole treatment liquid, as wellbore fluid or other downhole well applications.Figure 63 shows liquid 30 and combines as wellbore fluid with the drill bit 32 of drilling well 34.For wellbore fluid, get Syndril 810 (SD810) sample and mix with the TO phase of 5mM, wherein this sample is mineral oil.Mixture is placed in mixing tank and mixes 5 hours with the level of 1-40%, then continue mixing all night.Do not dissolve completely to morning sample, after therefore heating 30 minutes at 70 DEG C, TO is dissolved in sample mixture completely, again mixes 1 hour subsequently.Viscosity measured by the model grace model 35A 6 speed viscometer (Fann Model 35A 6speed Visometer) provided by the FANN INSTRUMENT company of Texas, Houston.In table 12 viscosity results is shown below, and shows that plastic viscosity is 10cP, and yield-point is 12lbs/100ft ².Wellbore fluid test show gained to mixture there is suitable viscosity and lower final rheological parameter (removing solid particulate).As above further as described in, after adding wetting agent (5mL/L) in the sample to which, repeat viscosity test.The viscosity results of the test subsequently of wetting agent sample see table 13 below, and shows that plastic viscosity is 10cP, and yield-point is 11.5lbs/100ft ².Drilling well compound is generally large amine, and this amine can not affect the aromatic series of acid amides branching and the hydrogen bonding effect of benzene four formaldehyde gel.Wellbore fluid comprises anti-phase.

Table 12: wellbore fluid test-results

Rotating speed (RPM)	Viscosity (cP)
		600/300	44/34
200/100	30/26
		6/3	21/19

Table 13: the wellbore fluid test-results adding wetting agent

Rotating speed (RPM)	Viscosity (cP)
		600/300	43/33
200/100	29/24
		6/3	20/18

Table 14 illustrates that the further test completed by wellbore fluid (adds the TO of 5mM, and with acceleration dust (rev dust) and wetting agent Dynol in SD810 ^tM604), and show that plastic viscosity is 17cP, and yield-point is 10.5lbs/100ft ².

Table 14: the wellbore fluid result adding wetting agent

Rotating speed (RPM)	Viscosity (cP)
		3	18
6	19
		100	26
200	32
		300	38
600	55

Table 15 illustrates the viscosity test of viscosity compared with other wellbore fluid various TO gel of 5mM being placed in SD810.Table 16 indicates the test-results of the composition be present in drilling mud.Under 25 DEG C of conditions, carry out viscosity and ES measure, and 100 DEG C, carry out fluid loss under the pressure reduction of 500psi.As can be seen, SD810 wellbore fluid, compared with other similar drilling mud, has higher viscosity.

Other wellbore fluid assessment of table 15:DF-48

Table 16: the component of wellbore fluid in table 15

Various N, N ', the variant of N ", N " '-(benzene-1,2,4,5-tetra-base) is tested, and gelling in the SynDril810 of 5mM, result is shown in table 17.

Table 17 is four acid amides viscosity in SynDril810 (SD810).

Gel title	Viscosity (cP)
		N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) heptamide	96-98
N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) decoylamide	87-89
		N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) pelargonamide	85-87
N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) decyl amide	78-79
		N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) lauramide	16-18
N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) myristamide	8-10
		N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) palmitamide	71-73

Table 18 below illustrates that wellbore fluid (SD810) is with TO and with the viscosity test results of added gel enhancing agent (i.e. hexa-methylene diamino chlorine) (hexanediamine dihydrochloride).Add the toughener of 9.6mM (it is equivalent to the 80mM with 10mM gel) to it prepare gel by the concentration of 1.2mM (2.4kg/m3).Result shows good low side rheological, such as, under the setting of 6/3.Such result shows that therefore liquid has cleaning capacity under low flow rate because gel keeps enough viscosity.

Table 18: the viscosity of the wellbore fluid of enhancing

Base fluid, except containing hydrocarbon compound, also can contain other liquid.Such as, base fluid comprises one or more in nitrogen or carbonic acid gas.Further, such as N2 can account for 50-95%, and CO2 can account for 5-50%.Also other scope and other base fluid can be adopted.In some cases, hydrocarbon compound base fluid can with other liquid mixing of such as N2 and CO2.

Gel enhancing agent

The conclusion that the discovery increasing instead of reduce the compound of benzene tetramethyl amide gellant viscosity causes is that the aromatic series gel of benzene four methane amide and acid amides branching can be combined with this gel enhancing agent.Jelling agent and toughener use together and can promote and the amount reduced for obtaining gel needed for relative similar viscosity.

Suitable gel enhancing agent can be made.Such as, gel enhancing agent can comprise metallic compound, potassium tert.-butoxide, diethanolamine, MENTHOL, lactic acid, amygdalic acid, ammonium acetate, paraformaldehyde, Resorcinol, and one or more in tetramethylammonium hydroxide.

Potassium tert.-butoxide and piperazine are tested as gel enhancing agent.The object performing test is whether the gel will determining to be enhanced can by broken glue.Solution is prepared by the TH of the gelling be included in TG740 hydrocarbon compound solution and a small amount of potassium tert.-butoxide or piperazine.For these solution five kinds of gel breakers, i.e. benzyl trimethyl ammonium chloride, 2-ethyl-n-butyl alcohol, 2-ethyl-1-hexylamine, benzylamine, and n-butyl alcohol is tested.These gel breakers can be used for destroying the hydrogen bond structure in the hydrocarbon compound solution of the gelling of standard well, and are used for now determining the validity in these thickening solutions.In the solution of non-reinforcing, these gel breakers make viscosity turn back to the viscosity of initial hydrocarbon compound immediately.By the existence of potassium tert.-butoxide, benzyl three fourth ammonium muriate, 2-ethyl-n-butyl alcohol, and n-butyl alcohol upon mixing viscosity reduce immediately.But 2-ethyl-1-hexylamine only reduces viscosity slightly, and benzylamine does not significantly reduce viscosity.For piperazine, benzyl three fourth ammonium muriate, 2-ethyl-n-butyl alcohol, benzylamine, and n-butyl alcohol upon mixing viscosity significantly reduce, and 2-ethyl-1-hexylamine only reduces viscosity slightly.All these gel breakers act on all well in enhancing solution with the solution in non-reinforcing.2-Ethylhexyl Alcohol also can be used as gel breaker.

After noticing piperazine thickening solution and increase the viscosity of the solution of gelling, the amount of carrying out some tests to check using piperazine whether can reduce benzene tetramethyl amide gellant still gives identical relative viscosity level simultaneously.The viscosity of various composition is determined and carry out the solution that comparative standard gelating soln is 8.0 mmoles (mmol) of TH solution (hydrocarbon compound is 24 milligrams in the TG 740 of 5mL).First piperazine (3.1mg/5 milliliter) gelating soln to 10% of four acid amides of 0.8 mmole (2.4 milligrams/5 milliliters) and 7.2 mmoles is used to test.This ratio seems not have the viscosity increasing solution compared to original hydrocarbon compound gelating soln, even when adding excessive piperazine (compared to the piperazine of four acid amides up to 12 times), this shows to exist the certain base concentration solution of at least 50% (the such as next test) of four acid amides, significantly to strengthen.With four acid amides (12 milligrams/5 milliliters) of 4.0 mmoles and 4.0 mmole piperazines (1.7 milligrams/5 milliliters) to next 50% gelating soln test.Solution becomes thicker compared to original hydrocarbon compound, but thick like that not as four acid amides gelling solns of 8 mmoles of standard.With four acid amides (12 milligrams/5 milliliters) of 4.0 mmoles and the piperazine (3.4 milligrams/5 milliliters) of 8.0 mmoles, the gelating soln to next 1: 2 ratio is tested.Compared to last test, the amount of piperazine doubles the viscosity increasing solution, makes solution approximately thick as four amide solution of 8.0 mmoles of standard.With four acid amides (12 milligrams/5 milliliters) of 4.0 mmoles and 12.0 mmole piperazines (5.1 milligrams/5 milliliters), the gelating soln to next 1: 3 ratio is tested.This gel seems to have effect slightly to increasing viscosity, but solution is thick like that not as the gel of 1: 2 ratio, and this may show that piperazine also can be used as gel breaker, the thickening solution when adding a small amount of, but breaks glue to solution when overdosed subsequently.With four acid amides (14.4 milligrams/5 milliliters) of 4.8 mmoles and the piperazine (1.38 milligrams/5 milliliters) of 3.2 mmoles, the gelating soln to the next one 60% is tested.This combination significantly increases the viscosity of solution, equally thick or slightly thicker with 8 mmole four amide solution of normally used standard.Finally, test with four acid amides (19.2 milligrams/5 milliliters) of 6.4 mmoles and piperazine (0.68 milligram/5 milliliters) gelating soln to 80% of 1.6 mmoles.This combination adds viscosity compared to four amide solution of 8 mmoles of standard.In some cases, gel enhancing agent can toughener: gel be 1: 1 or 50% ratio exist or exist with the ratio higher than above-mentioned ratio.

Some other molecules are tested so that the TH gelating soln detecting them thickening (enhancing) is conventional.The three kinds of chemical realizing this result are MENTHOLs, paraformaldehyde and Resorcinol.The composition of the former gelating soln of 8 mmoles (being 24 milligrams in the hydrocarbon compound of 5ml) is changed and can uses four less acid amides whether less and the viscosity not reducing gelating soln to detect thus.Often kind of chemical is tested in three kinds of different compositions: 1) 50: 50 solution: four acid amides of 4.0 mmoles in the hydrocarbon compound at 5ml, other chemical all of 4.0 mmoles; 2) 60: 40 solution: four acid amides of 4.8 mmoles in the hydrocarbon compound of 5ml, other chemical all of 3.2 mmoles; 3) 80: 20 solution: four acid amides of 6.4 mmoles in the hydrocarbon compound of 5ml, other chemical all of 1.6 mmoles.For MENTHOL, described first composition does not almost affect viscosity, and the second composition causes viscosity slightly to increase, and the viscosity of the 3rd composition is almost identical with four amide solution of 8 mmoles of standard.Similarly paraformaldehyde is tested with MENTHOL.For quinhydrones, first composition does not almost affect viscosity, second composition increases viscosity more than other two kinds of compounds, but still do not reach the viscosity same with 8 mmole solution of standard, and the 3rd composition identical with the viscosity of 8 mmole solution of standard, and larger than the viscosity caused by other two kinds of compounds.

Although the most effective thickening materials of Resorcinol seemingly these three kinds tests, the gel with 80: 20: the ratio of toughener shows the viscosity being equivalent to 100: 0 ratios, these three kinds of chemical are all not so good as piperazine and work well in this respect.But result shows that heterogeneous ring compound (such as having Isosorbide-5-Nitrae-relation) can work as gel enhancing agent, but piperazine and quinhydrones seem increase viscosity for tested all compounds.Therefore, gel enhancing agent can comprise cyclic heterocycle in certain embodiments, such as, have and be spaced apart from each other and the heterocycle of each at least two heteroatomss (be not all carbon neither hydrogen) with one or more pairs of lone-pair electron.As mentioned above, the example of the heterocycle of 6 atom rings is piperazines.In other embodiments, heterocycle can form the ring of 6 atoms, its have be positioned at 1 and 4 places or be positioned at start from 1 and 4 corresponding functional group on two non-carbon.The comparable oxygen donor of nitrogen donor works better, and this is probably the low electronegativity due to nitrogen, and this makes its orphan larger to polarity, and forms stronger hydrogen bond.The linking agent of heterocycle or other type is considered to be similar to the mode of clay gall in drilling well and works, and its reason is the both sides of this compound energy hydrogen bonding to compound, thus is linked to together by two adjacent gel chains.

As other place in the application confirm, by being tested as the additive adding four acrylamide gel solution to tetramethyl-oxyhydroxide by 4-n-butyl ammonium hydroxide, whether there is brokenly glue or enhancing to detect.Once add, 4-n-butyl ammonium hydroxide breaks glue to gelating soln, but Tetramethylammonium hydroxide thickening solution, and thus demonstrate two kinds of different results, this may be that the different chain length of alkyl owing to being attached to nitrogen-atoms causes.Be similar to piperazine, by replacing the part of gel to test the effect of Tetramethylammonium hydroxide by Tetramethylammonium hydroxide so that detect whether can when using four less acrylamide gel while keep viscosity.As previously mentioned, the benchmark for viscosity is the solution (four acid amides are 24 milligrams in TG 740 hydrocarbon compound of 5 milliliters) of 8 mmoles.The first tested composition is the solution of 50: 50: four acid amides of 4.0 mmoles all in 5 milliliters of hydrocarbon compounds, the Tetramethylammonium hydroxide of 4.0 mmoles.Said composition causes viscosity slightly to increase with the level being similar to other gel enhancing agent.The composition of following test is the solution of 60: 40: four acid amides of 4.8 mmoles in 5 milliliters of hydrocarbon compounds, other chemical all of 3.2 mmoles.Said composition demonstrates the result similar with 50: 50 compositions.The composition of last test is the solution of 80: 20: four acid amides of 6.4 mmoles in 5 milliliters of hydrocarbon compounds, other chemical all of 1.6 mmoles.Equally, said composition does not cause very large change in viscosity, although this solution keeps being thick, thick like that not as four acrylamide gel solution of 8 mmoles of standard.On the whole, Tetramethylammonium hydroxide is not too effective compared to piperazine, but really shows that some four acid amides replace by other chemical, and does not reduce viscosity.

The metallic compound gel enhancing agent of such as metal-salt can comprise positively charged ion, such as one or more iron and aluminium.Described cat ions as by using one or more tensio-active agent chelatings and can complexing, to improve the solubleness in base fluid.For example, referring to Figure 58-60, with the Fe-activator that different measurements examination is iron (III) sulphate form in DF-46 gel, its HGA-65 sold by Weatherford International provides.HGA-65 is a kind of organometallic complex, its traditionally for the phosphoric acid ester jelling agent in hydrocarbon compound fracturing liquid as activator.HGA-65 contains citric acid, and amine.Figure 58 shows and add gel enhancing agent after gel formation, and confirms that more toughener is equivalent to larger viscosity.Figure 59 illustrates that adding gel enhancing agent can accelerate gelling.Figure 60 illustrates that the concentration when benzene tetramethyl amide gellant decreases beyond predetermined concentration or concentration range, then positive effect may reduce.By the ferric sulfate success unexpectedly of complexing, because pure ferric sulfate demonstrates have broken glue effect to gel.But, iron positively charged ion is pulled in the solution in hydrocarbon compound base fluid by the complexing agent being considered to be provided with ferric sulfate, and make iron positively charged ion close to gellant molecules, may to occur with gel molecular close to part crosslinked above-mentioned, or iron can improve the stability of the hydrogen bond between gel molecular.The broken glue effect of pure ferric sulfate is considered to because jelling agent pulls out by the polar forces of polarity ferric sulfate super large from the solution with base fluid.

Also can use other metallic compound, such as polyvalent metal salt, comprises zinc.It is believed that gel enhancing agent is by being cross-linked adjacent gel molecular or being worked by the cross linking hydrogen bonds between promotion adjacent gel molecule.Gel enhancing agent can be provided with the tensio-active agent for being dispersed in by gel enhancing agent in base fluid, such as, when ferric sulfate, wherein there is Citrate trianion and amine.Dispersion is such as dissolved in solution and allows gel enhancing agent close to gel molecular to carry out required enhancing.In other cases, gel enhancing agent can be dissolved in base fluid by neat form.

Under normal circumstances, metalloid salt gel cross-linkage can be can be used as gel enhancing agent to provide the compound of other viscosity.Such as, Al3+, Fe3+ are tested and both can be used as gel enhancing agent.At higher concentrations, Complexing Iron (III) vitriol is poor as toughener meeting effect.Al3+ can the form of aluminum isopropylate provide, and wherein aluminum portions strengthens gelling and propylate can break glue, and as mentioned above, such viscosity profile comprises the peak in viscosity.Other metal alkoxide can be used as gel enhancing agent, and also can be used as gel breaker in some cases, and such as, the activable gel breaker of water, its hydrate be arranged in liquid is combined, to discharge water and alkoxide is become alcohol.In some cases, alkoxide is excluded as outside gel enhancing agent.

As mentioned above, jelling agent by adjacent gellant molecules acid amides branch between intermolecular hydrogen bonding form hydrogen bond structure.Gel enhancing agent is by being cross-linked intermolecular hydrogen bonding or promoting intermolecular hydrogen bonding and strengthen gelling.Be cross-linked and realize by hydrogen bond bridge joint Liang Ge acid amides branch and toughener.Promotion can comprise the direct hydrogen bond between stable acid amides branch.

Gel enhancing agent can comprise aromatic carboxylic acid salt, such as ibuprofen salt (table 0).Other salt comprises hydrocinnamoyl hydrochlorate, diphenyl acetic acid salt, benzoate and phenylacetate.It is believed that COO-hydrogen bonding (is cross-linked) between acid amides branch, and the aromatic group on toughener and the aromatic group on gel interact, stable gel.As mentioned above, the comparable COOH of COO-salt is more water miscible, and this salt only can keep relatively low concentration in the hydrocarbon phase with gel thus.By contrast, the protonated COOH group of aromatic carboxylic acid can be used as the gel breaker of gel, see above.

As mentioned above, gel enhancing agent also can operate as gel breaker under the configuration of different conditioned disjunctions.An example of the gel breaker/toughener of dual-use function is aromatic carboxylic acid.Properties-correcting agent can be added in gel, and properties-correcting agent is selected to and gel enhancing agent is transformed into gel breaker.In some cases, gel enhancing agent exists with the concentration lower than threshold concentration in gel, if higher than threshold concentration, then gel enhancing agent just becomes gel breaker, and wherein said properties-correcting agent comprises the additional source being enough to the concentration of gel enhancing agent is elevated to the gel enhancing agent higher than threshold concentration.The example depending on the gel breaker/toughener of the dual-use function of concentration comprises piperidines (see table 0) and piperazine.The additional source of toughener can coated form provide to delay release.In other cases, properties-correcting agent can be chosen to existing gel enhancing agent carry out chemical modification chemical.Such as, if piperidines is used as toughener, then properties-correcting agent can comprise benzylamine.Further, if such as aromatic carboxylic acid salt is used as toughener, then properties-correcting agent can comprise the proton source of such as acid, or the cation complexing agents of such as citric acid.

Gel enhancing agent can be comprised ammonium chloride, trimeric cyanamide, choline chloride 60, and one or more in hexa-methylene diamino chlorine (table 0).Other toughener can be used.

In some cases, one or more (such as each) acid amides branch is connected to aromatic proton via carbon-nitrogen bond.Structure (8)-(12) are the examples of this jelling agent.Jelling agent can have three or four acid amides branches, and such as four acid amides branches, as follows.Each organic group can be alkyl such as C6-24 straight chained alkyl, as follows.Figure 64 illustrates the compound (8) of the 5mM at room temperature in TG740, the viscosity performance of (9) and (12).

Preparation N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) four hexanamides (8)

Program.By phenyl-1,2,4,5-tetra-ammonium muriate (2.0 grams, 7.0 mmoles), triethylamine (5.8cm3,42.0 mmoles) and anhydrous tetrahydro furan (150 milliliters) join and are equipped with in the round-bottomed flask of magnetic stirring apparatus, and fully mix until most of dissolution of solid.Caproyl chloride (4.9cm3,35.0 mmoles) is slowly joined in this solution, causes the pink color disappeared in solution and white precipitate to be formed.Solution is filtered, uses rotatory evaporator to remove solvent, orange solids crude product is dissolved in toluene (50 milliliters), and dropwise adds in ethanol (200 milliliters) solution of vigorous stirring, so that product carries out redeposition.White solid is leached and drying under vacuo, to obtain product (2.43 grams, 61.8%) needed for somewhat viscous pale solid.

Preparation N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) four heptamides (9)

Program.By phenyl-1,2,4,5-tetra-ammonium muriate (1.0 grams, 3.5 mmoles), triethylamine (2.8cm3,20.0 mmoles) and anhydrous tetrahydro furan (50 milliliters) join and are equipped with in the round-bottomed flask of magnetic stirring apparatus, and fully mix until most of dissolution of solid.Oenanthyl chloro (2.3cm3,15.0 mmoles) is slowly joined in this solution, causes rediance solution become brown and form throw out.Solution is filtered, uses rotatory evaporator to remove solvent, obtain orange solids, to be dissolved in toluene (30 milliliters) and to join in ethanol (200 milliliters) solution of vigorous stirring, to carry out redeposition to product.White solid is leached and drying under vacuo, obtain the required product (0.88 gram, 43.0%) of the pale solid of somewhat viscous.

Preparation N, N ', N ", N " '-(phenyl-1,2,4,5-tetra-base) four decoylamides (10)

Program.By phenyl-1,2,4,5-tetra-ammonium muriate (1.0 grams, 3.5 mmoles), triethylamine (during 2.8cm3,20.0 mmoles) and anhydrous tetrahydro furan (50 milliliters) join and are equipped with in the round-bottomed flask of magnetic stirring apparatus, and fully mix until most of dissolution of solid.Capryl(yl)chloride (2.5cm3,15.0 mmoles) is slowly joined in this solution, causes rediance solution become brown and form throw out.Solution is filtered, uses rotatory evaporator to remove solvent, obtain orange solids, to be dissolved in toluene (30 milliliters) and to join in ethanol (200 milliliters) solution of vigorous stirring, to carry out redeposition to product.White solid is leached and drying under vacuo, obtain product (1.17 grams, 51.7%) needed for pale solid.

Preparation N, N ', N ", N " '-(benzene-1,2,4,5-tetra-base) four pelargonamides (11)

Process.By phenyl-1,2,4,5-tetra-ammonium muriate (1.0 grams, 3.5 mmoles), triethylamine (during 2.8cm3,20.0 mmoles) and anhydrous tetrahydro furan (50 milliliters) join and are equipped with in the round-bottomed flask of magnetic stirring apparatus, and fully mix until most of dissolution of solid.Decanoyl chloride (3.1cm3,15.0 mmoles) is slowly joined in this solution, causes rediance solution become brown and form throw out.Solution is filtered, uses rotatory evaporator to remove solvent, obtain orange solids, to be dissolved in toluene (30 milliliters) and to join in ethanol (200 milliliters) solution of vigorous stirring, to carry out redeposition to product.White solid is leached and drying under vacuo, obtain product (1.24 grams, 46.6%) needed for pale solid.

Preparation N, N ', N ", N " '-(benzene-1,2,4,5-tetra-base) four lauramides (12)

program.By phenyl-1,2,4,5-tetra-ammonium muriate (1.0 grams, 3.5 mmoles), triethylamine (2.8cm3,20.0 mmoles) and anhydrous tetrahydro furan (50 milliliters) join and are equipped with in the round-bottomed flask of magnetic stirring apparatus, and fully mix until most of dissolution of solid.Dodecane acyl chlorides (3.6cm3,15.0 mmoles) is slowly joined in this solution, causes rediance solution become brown and form throw out.Solution is filtered, uses rotatory evaporator to remove solvent, obtain orange solids, to be dissolved in toluene (30 milliliters) and to join in ethanol (200 milliliters) solution of vigorous stirring, to carry out redeposition to product.White solid is leached and drying under vacuo, obtain product (1.34 grams, 44.0%) needed for pale solid.

Table 19: N, N ', N ", N " percentage yield, fusing point and the viscosity number of '-(phenyl-*) gel

In certain embodiments, jelling agent has compound form (13) below or (14), wherein R represents the alkyl or hydrocarbyl group with 1-29 carbon atom independently, and R1 represents the hydrocarbyl group with 1-29 carbon atom independently.Number be 6,645, disclosing other example of these and other suitable jelling agent in the United States Patent (USP) of 577, which depict the compound of gel formation.Thus this compound is considered to be suitable for using together with down-hole liquid.A kind of synthesis example of such compound (15) is described in detail as follows.

Program.In the tetrahydrofuran (THF)s of 70 milliliters (THF), dissolve 1,3, the 5-benzenetricarboxylic acid of 0.7 gram and the tristearin of 2.5 grams.1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride (WSC: water-soluble carbodiimide) of 3.6 grams and 1-hydroxyl-1H-benzotriazole (HOBT) of 2.53 grams are joined in this solution, on ice bath, then dropwise adds the triethylamine (TEA) of 5 milliliters.After the addition, mixture stir by ice bath 2 hours and at room temperature stir further.By filtering and being dissolved in chloroform, reaction mixture is reclaimed.With dilute hydrochloric acid, sodium bicarbonate aqueous solution and water successive wash subsequently.Product anhydrous sodium sulfate drying also carries out recrystallization, obtains the object compound (15) as implied above of 4.0g gram.

In certain embodiments, one or more acid amides branch is connected to aromatic proton via C-C, and one or more acid amides branch is connected to aromatic proton via carbon-nitrogen bond.The example with this structure of the ratio that different N-C with C-C is connected comprises compound form (16)-(18) below:

In the embodiment of superincumbent (16)-(18), independent of R1, R2 and R3 each other, or Y1, Y2 and Y3, or Z1, Z2 and Z3 are the C1-C20 alkyl not being substituted or being optionally substituted with one or more hydroxyl replacement; Be not substituted or be optionally substituted with one or more hydroxyl the C2-C20 alkenyl of replacement; The C2-C20 alkyl interrupted by oxygen or sulphur; The C3-C12 cycloalkyl not being substituted or being replaced by one or more C1-C20 alkyl; (C3-C12 the cycloalkyl)-C1-C10 alkyl not being substituted or being replaced by one or more C1-C20 alkyl; Two [C3-C12 the cycloalkyl]-C1-C10 alkyl not being substituted or being replaced by one or more C1-C20 alkyl; Two rings with 5 to 20 carbon atoms be not substituted or replaced by one or more C1-C20 alkyl or tricyclic hydrocarbon base; The phenyl not being substituted or being replaced by one or more group, described one or more group is selected from C1-C20 alkyl, C1-C20 alkoxyl group, C1-C20 alkyl amine group, and two (C1-C20 alkyl) is amino, hydroxyl and nitro; Phenyl-C1-C20 the alkyl be not substituted or replaced by one or more group, described one or more group is selected from C1-C20 alkyl, C3-C12 cycloalkyl, phenyl, C1-C20 alkoxyl group and hydroxyl; The phenyl vinyl not being substituted or being replaced by one or more C1-C20 alkyl; Biphenyl-(the C1-C10 alkyl) not being substituted or being replaced by one or more C1-C20 alkyl; The naphthalene not replacing or replaced by one or more C1-C20 alkyl; Naphthyl-C1-C20 the alkyl not being substituted or being replaced by one or more C1-C20 alkyl; Naphthyloxymethyl that is unsubstituted or that replaced by one or more C1-C2 alkyl; Xenyl, fluorenes, anthracene; 5-to the 6-unit heterocyclic radical not being substituted or being replaced by one or more C1-C20 alkyl; C1-C20 alkyl containing one or more halogen; Or three (C1-C10 alkyl) silyl (C1-C10 alkyl); Wherein collateral condition is radicals R 1, R2 and R3, or Y1, Y2 and Y3, or at least one in Z1, Z2 and Z3 is the side chain C3-C20 alkyl not being substituted or being optionally substituted with one or more hydroxyl replacement; The C2-C20 alkyl interrupted by oxygen or sulphur; The C3-C12 cycloalkyl not being substituted or being replaced by one or more C1-C20 alkyl; (C3-C12 the cycloalkyl)-C1-C10 alkyl not being substituted or being replaced by one or more C1-C20 alkyl; Two rings with 5 to 20 carbon atoms be not substituted or replaced by one or more C1-C20 alkyl or tricyclic hydrocarbon base; The phenyl not being substituted or being replaced by one or more group, described one or more group is selected from C1-C20 alkyl, C1-C20 alkoxyl group, C1-C20 alkyl amine group, and two (C1-C20 alkyl) is amino, hydroxyl and nitro; Phenyl-C1-C20 the alkyl be not substituted or replaced by one or more group, described one or more group is selected from C1-C20 alkyl, C3-C12 cycloalkyl, phenyl, C1-C20 alkoxyl group and hydroxyl; Biphenyl-(the C1-C10 alkyl) not being substituted or being replaced by one or more C1-C20 alkyl; Naphthyl-C1-C20 the alkyl not being substituted or being replaced by one or more C1-C20 alkyl; Or three (C1-C10 alkyl) silyl (C1-C10 alkyl).

Number be 7,790, disclose (16)-other the example of (18) and other suitable jelling agent in 793d United States Patent (USP), which depict for the preparation of gel stick and improve the jelling agent of the gel stability of the system based on water and organic solvent.Thus this jelling agent is considered to be suitable for using together with down-hole liquid.A kind of synthesis example of such compound (19) is described in detail as follows.

1,3, the 5-triaminobenzene trihydrochloride (see example A) of 1.00g (4.3 mmole) and the lithium chloride of 0.1 gram are joined the anhydrous pyridine of 50 milliliters anhydrous NMP and 10 milliliter under an inert atmosphere and be cooled to 5 degrees Celsius.Add the pivalyl chloride (14.3 mmole) of 1.73 grams.Reaction mixture is heated to 60 degrees Celsius, and stirs.After 24 hours, reaction mixture is added in the frozen water of 1000ml.Throw out is leached.Usual aftertreatment (from tetrahydrofuran (THF) recrystallization) obtains required product (19).

As implied above, jelling agent can have the phenyl ring as aromatic proton.But, also can use other aromatic proton.Such as, naphthalene can be used as aromatic proton.Aromatic proton can be smooth, and wishes the formation promoting above-mentioned lamellar gel mechanism.

As implied above, each acid amides branch can have an organic group or side chain.But in some cases, one or more acid amides branch has two organic groups.Such as, acid amides branch is connected to aromatic proton via carbon-nitrogen bond, and nitrogen has alkyl group and carbonyl carbon has organic group.Other example can be used.One or more acid amides branch can have two organic groups on amide nitrogen, as long as at least one, two, or multiple acid amides branch has with free hydrogen so that hydrogen-bonded amide nitrogen.In other cases, each acid amides branch nitrogen has a hydrogen atom, farthest to promote hydrogen bonding and gel formation.

Non-alkyl organic side chain can be used.The organic group with five or less carbon atoms can be used.

In the claims, word " comprises " and using with the implication of its inclusive, but does not get rid of also to comprise and there is other element.Add before the feature of claim indefinite article " (a) " do not get rid of comprise more than one feature exist.Each personal feature as herein described can, with in one or more embodiments, just should not be considered to be absolutely necessary to all embodiments defined by the claims owing to being only described herein.

Claims (amendment according to treaty the 19th article)

1. a liquid, it comprises base fluid, jelling agent and gel enhancing agent, wherein jelling agent has the aromatic proton of one or more aromatic nucleus, jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branches has one or more organic group.

2. liquid according to claim 1, wherein gel enhancing agent comprises organic molecule, and it has at least two heteroatomss being spaced apart from each other and having one or more pairs of lone-pair electron separately.

3. liquid according to claim 2, wherein organic molecule is heterocycle.

4. liquid according to claim 3, wherein said heterocycle forms the ring of 6 atoms, its have be positioned at 1 and 4 places or be positioned at start from 1 and 4 corresponding functional group on two non-carbon.

5. liquid according to claim 4, wherein said heterocycle comprises piperazine.

6. the liquid according to any one of claim 1 to 5, wherein said gel enhancing agent comprises metallic compound, potassium tert.-butoxide, diethanolamine, MENTHOL, lactic acid, amygdalic acid, ammonium acetate, paraformaldehyde, Resorcinol, and one or more in tetramethylammonium hydroxide.

7. liquid according to claim 6, is wherein provided with metallic compound and it comprises one or more iron and aluminium.

8. the liquid according to any one of claim 1 to 7, also comprises the tensio-active agent for being distributed to by gel enhancing agent in base fluid.

9. liquid according to claim 8, wherein gel enhancing agent comprises iron (III) vitriol.

10. the liquid according to any one of claim 1 to 7, also comprises the tensio-active agent for being distributed to by gel enhancing agent in base fluid.

11. liquid according to claim 10, the gel enhancing agent in wherein said tensio-active agent and base fluid forms complex compound.

12. liquid according to any one of claim 6 to 7, wherein said metallic compound can be dissolved in base fluid by neat form.

13. liquid according to claim 12, wherein said metallic compound comprises metal alkoxide.

14. liquid according to claim 13, wherein said metal alkoxide comprises aluminum isopropylate.

15. liquid according to any one of claim 1 to 14, wherein said gel enhancing agent comprises aromatic carboxylic acid salt.

16. liquid according to claim 15, wherein said aromatic carboxylic acid salt comprises ibuprofen salt.

17. liquid according to any one of claim 1 to 16, wherein said gel enhancing agent comprises ammonium chloride, trimeric cyanamide, choline chloride 60, and one or more in hexa-methylene diamino chlorine.

18. liquid according to any one of claim 1 to 14, wherein said jelling agent forms hydrogen bond structure by the intermolecular hydrogen bonding between the acid amides branch of adjacent gellant molecules, and wherein gel enhancing agent is crosslinked or promote intermolecular hydrogen bonding by intermolecular hydrogen bonding.

19. liquid according to claim 18, also comprise the properties-correcting agent being chosen to gel enhancing agent is transformed into gel breaker.

20. liquid according to claim 19, wherein be provided with the gel enhancing agent lower than threshold concentration, if higher than this threshold concentration, then gel enhancing agent just becomes gel breaker, and wherein said properties-correcting agent comprises the additional source being enough to the concentration of gel enhancing agent is elevated to the gel enhancing agent higher than threshold concentration.

21. liquid according to claim 20, wherein said gel enhancing agent comprises piperidines or piperazine.

22. liquid according to any one of claim 20 to 21, wherein said gel enhancing agent comprises piperidines and properties-correcting agent comprises benzylamine.

23. according to claim 19 to the liquid described in 21 any one, and wherein said gel enhancing agent comprises aromatic carboxylic acid salt, and wherein said properties-correcting agent comprises proton source or cation complexing agents.

24. liquid according to claim 23, wherein said proton source comprises acid.

25. liquid according to claim 23, wherein said cation complexing agents comprises citric acid, and aromatic carboxylic acid salt comprises ibuprofen salt.

26. according to claim 19 to the liquid described in 25 any one, and wherein said described properties-correcting agent also comprises coating layer.

27. liquid according to any one of claim 1 to 26, wherein each acid amides branch is connected to aromatic proton via carbon-to-carbon or carbon-nitrogen bond.

28. liquid according to claim 27, wherein one or more acid amides branches are connected to aromatic proton via carbon-nitrogen bond.

29. liquid according to claim 28, wherein each acid amides branch is connected to aromatic proton via carbon-nitrogen bond.

30. liquid according to any one of claim 1 to 29, have four acid amides branches.

31. liquid according to any one of claims 1 to 30, wherein each organic group is alkyl group.

32. liquid according to claim 31, wherein each alkyl group is linear alkyl groups.

33. liquid according to any one of claim 31 to 32, wherein each alkyl group has 6-24 carbon atom.

34. liquid according to any one of claims 1 to 33, wherein aromatic proton is phenyl ring.

35. liquid according to claim 34, wherein each acid amides branch is connected to aromatic proton via carbon-nitrogen bond, and each organic group is the alkyl group with 6-24 carbon atom.

36. liquid according to claim 34, wherein one or more acid amides branches are connected to aromatic proton via C-C, and one or more acid amides branch is connected to aromatic proton via carbon-nitrogen bond.

37. liquid according to any one of claim 35 to 36, wherein each alkyl group has 6-12 carbon atom.

38. liquid according to any one of claim 34 to 37, have three or four acid amides branches.

39. liquid according to any one of claims 1 to 38, wherein aromatic proton is naphthalene nucleus.

40. liquid according to any one of claims 1 to 39, wherein each acid amides branch has an organic group.

41. liquid according to any one of Claims 1-4 0, wherein get rid of benzene tetramethyl amide gellant.

42. liquid according to any one of Claims 1-4 0, wherein jelling agent is benzene tetramethyl amide gellant and has following general formula:

43. liquid according to claim 42, wherein R ₅, R ₆, R ₇and R ₈in be eachly respectively hydrogen, and one or more R ₁, R ₂, R ₃and R ₄in each be alkyl group.

44. liquid according to claim 43, wherein R ₁, R ₂, R ₃and R ₄in be eachly respectively alkyl group.

45. liquid according to claim 44, wherein R ₁=R ₂=R ₃=R ₄.

46. liquid according to claim 45, wherein R ₁, R ₂, R ₃and R ₄in each there are at least 6 carbon atoms.

47. liquid according to any one of claim 44 to 45, wherein each alkyl group has 6-24 carbon atom.

48. liquid according to claim 47, wherein each alkyl group has 6-10 carbon atom.

49. liquid according to any one of claim 43 to 48, wherein each alkyl group is one or more straight chain group, branched group or cyclic group.

50. liquid according to claim 49, wherein each alkyl group is straight chain group.

51. liquid according to claim 50, wherein R ₅, R ₆, R ₇and R ₈in each be hydrogen respectively, and R ₁, R ₂, R ₃and R ₄in each be the linear alkyl groups with 6-10 carbon atom respectively.

52. liquid according to claim 51, wherein R ₁, R ₂, R ₃and R ₄there are 6 carbon atoms.

53. liquid according to any one of claim 1 to 52, wherein base fluid comprises hydrocarbon compound.

54. liquid according to claim 53, wherein hydrocarbon compound has 3-8 carbon atom.

55. liquid according to any one of claim 1 to 54, also comprise gel breaker.

56. liquid according to claim 55, wherein said gel breaker comprises one or more bromide salt, chloride salt, organic salt and amine salt further.

57. liquid according to any one of claim 55 to 56, wherein said gel breaker comprises one or more ethanol or alkoxide.

58. liquid according to claim 57, ethanol described in wherein one or more or alkoxide have 2 or multiple carbon atom.

59. liquid according to claim 58, are wherein provided with alkoxide and alkoxide comprises aluminum isopropylate.

60. liquid according to any one of claim 55 to 59, wherein gel breaker is that water activates gel breaker and liquid comprises hydrate.

61. liquid according to any one of claim 55 to 60, wherein gel breaker comprises coating layer further.

62. liquid according to claim 61, wherein said coating layer comprises wax further.

63. 1 kinds of methods, comprise and the liquid according to any one of claim 1 to 62 are used as wellbore fluid.

64. methods according to claim 63, wherein gel enhancing agent comprises hexa-methylene diamino chlorine.

65. 1 kinds of methods, comprise the liquid according to any one of claim 1 to 63 with dealing with fluid.

66. for the method by liquid according to any one of claim 1 to 65 being prepared by base fluid, jelling agent, gel enhancing agent combination.

67. 1 kinds of liquid, it comprises base fluid, jelling agent and gel breaker, wherein jelling agent has the aromatic proton of one or more aromatic nucleus, described jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branch has one or more organic group.

68. liquid according to claim 67, wherein said gel breaker comprises aromatic carboxylic acid.

69. liquid according to claim 68, wherein said gel breaker comprise in Ibuprofen BP/EP and phenylpropionic acid one or more.

70. liquid according to any one of claim 68 to 69, wherein said gel breaker comprise in diphenyl acetic acid, phenylformic acid and toluylic acid one or more.

71. liquid according to any one of claim 68 to 70, also comprise cation complexing agents, wherein aromatic carboxylic acid is salt.

72. according to the liquid described in claim 71, and wherein said aromatic carboxylic acid comprises ibuprofen salt, and cation complexing agents comprises citric acid.

73. liquid according to any one of claim 67 to 72, wherein said jelling agent forms hydrogen bond structure by the intermolecular hydrogen bonding between the acid amides branch of adjacent gellant molecules, and hydrogen bond between gel breaker saboteur wherein.

74. according to the liquid described in claim 73, and wherein said described gel breaker is the hydrogen bonding agent forming hydrogen bond with the acid amides branch of jelling agent, described hydrogen bond than adjacent gellant molecules acid amides branch between intermolecular hydrogen bonding stronger.

75. liquid according to claim 1 to 62 and 67 to 74 any one, wherein base fluid comprises liquefied petroleum gas (LPG).

76. liquid according to claim 47, wherein each alkyl group has 7-24 carbon atom.

77. liquid according to claim 28, have four or multiple acid amides branches.

78. according to the liquid described in claim 77, has four acid amides branches.

79. 1 kinds of methods, comprise and the liquid according to claim 1 to 62 and 67 to 78 any one are used as downhole fluid.

80. liquid according to claim 1 to 62 and 67 to 78 any one, wherein said liquid is downhole fluid.

Claims

1. a down-hole liquid, it comprises base fluid, jelling agent and gel enhancing agent, wherein jelling agent has the aromatic proton of one or more aromatic nucleus, jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branches has one or more organic group.

2. down-hole liquid according to claim 1, wherein gel enhancing agent comprises organic molecule, and it has at least two heteroatomss being spaced apart from each other and having one or more pairs of lone-pair electron separately.

3. down-hole liquid according to claim 2, wherein organic molecule is heterocycle.

4. down-hole liquid according to claim 3, wherein said heterocycle forms the ring of 6 atoms, its have be positioned at 1 and 4 places or be positioned at start from 1 and 4 corresponding functional group on two non-carbon.

5. down-hole liquid according to claim 4, wherein said heterocycle comprises piperazine.

6. the down-hole liquid according to any one of claim 1 to 5, wherein said gel enhancing agent comprises metallic compound, potassium tert.-butoxide, diethanolamine, MENTHOL, lactic acid, amygdalic acid, ammonium acetate, paraformaldehyde, Resorcinol, and one or more in tetramethylammonium hydroxide.

7. down-hole liquid according to claim 6, is wherein provided with metallic compound and it comprises one or more iron and aluminium.

8. the down-hole liquid according to any one of claim 1 to 7, also comprises the tensio-active agent for being distributed to by gel enhancing agent in base fluid.

9. down-hole liquid according to claim 8, wherein said metallic compound comprises iron (III) vitriol.

10. the down-hole liquid according to any one of claim 1 to 7, also comprises the tensio-active agent for being distributed to by gel enhancing agent in base fluid.

11. down-hole liquids according to claim 10, the gel enhancing agent in wherein said tensio-active agent and base fluid forms complex compound.

12. down-hole liquids according to any one of claim 6 to 7, wherein said metallic compound can be dissolved in base fluid by neat form.

13. down-hole liquids according to claim 12, wherein said metallic compound comprises metal alkoxide.

14. down-hole liquids according to claim 13, wherein said metal alkoxide comprises aluminum isopropylate.

15. down-hole liquids according to any one of claim 1 to 14, wherein said gel enhancing agent comprises aromatic carboxylic acid salt.

16. down-hole liquids according to claim 15, wherein said aromatic carboxylic acid salt comprises ibuprofen salt.

17. down-hole liquids according to any one of claim 1 to 16, wherein said gel enhancing agent comprises ammonium chloride, trimeric cyanamide, choline chloride 60, and one or more in hexa-methylene diamino chlorine.

18. down-hole liquids according to any one of claim 1 to 14, wherein said jelling agent forms hydrogen bond structure by the intermolecular hydrogen bonding between the acid amides branch of adjacent gellant molecules, and wherein gel enhancing agent is crosslinked or promote intermolecular hydrogen bonding by intermolecular hydrogen bonding.

19. down-hole liquids according to claim 18, also comprise the properties-correcting agent being chosen to gel enhancing agent is transformed into gel breaker.

20. down-hole liquids according to claim 19, wherein be provided with the gel enhancing agent lower than threshold concentration, if higher than this threshold concentration, then gel enhancing agent just becomes gel breaker, and wherein said properties-correcting agent comprises the additional source being enough to the concentration of gel enhancing agent is elevated to the gel enhancing agent higher than threshold concentration.

21. down-hole liquids according to claim 20, wherein said gel enhancing agent comprises piperidines or piperazine.

22. down-hole liquids according to any one of claim 20 to 21, wherein said gel enhancing agent comprises piperidines and properties-correcting agent comprises benzylamine.

23. according to claim 19 to the down-hole liquid described in 21 any one, and wherein said gel enhancing agent comprises aromatic carboxylic acid salt, and wherein said properties-correcting agent comprises proton source or cation complexing agents.

24. down-hole liquids according to claim 21, wherein said proton source comprises acid.

25. down-hole liquids according to claim 21, wherein said cation complexing agents comprises citric acid, and aromatic carboxylic acid salt comprises ibuprofen salt.

26. according to claim 19 to the down-hole liquid described in 25 any one, and wherein said described properties-correcting agent also comprises coating layer.

27. down-hole liquids according to any one of claim 1 to 26, wherein each acid amides branch is connected to aromatic proton via carbon-to-carbon or carbon-nitrogen bond.

28. down-hole liquids according to claim 27, wherein one or more acid amides branches are connected to aromatic proton via carbon-nitrogen bond.

29. down-hole liquids according to claim 28, wherein each acid amides branch is connected to aromatic proton via carbon-nitrogen bond.

30. down-hole liquids according to any one of claim 1 to 29, have four acid amides branches.

31. down-hole liquids according to any one of claims 1 to 30, wherein each organic group is alkyl group.

32. down-hole liquids according to claim 31, wherein each alkyl group is linear alkyl groups.

33. down-hole liquids according to any one of claim 31 to 32, wherein each alkyl group has 6-24 carbon atom.

34. down-hole liquids according to any one of claims 1 to 33, wherein aromatic proton is phenyl ring.

35. down-hole liquids according to claim 34, wherein each acid amides branch is connected to aromatic proton via carbon-nitrogen bond, and each organic group is the alkyl group with 6-24 carbon atom.

36. down-hole liquids according to claim 35, wherein one or more acid amides branches are connected to aromatic proton via C-C, and one or more acid amides branch is connected to aromatic proton via carbon-nitrogen bond.

37. down-hole liquids according to any one of claim 35 to 36, wherein each alkyl group has 6-12 carbon atom.

38. down-hole liquids according to any one of claim 34 to 37, have three or four acid amides branches.

39. down-hole liquids according to any one of claims 1 to 38, wherein aromatic proton is naphthalene nucleus.

40. down-hole liquids according to any one of claims 1 to 39, wherein each acid amides branch has an organic group.

41. down-hole liquids according to any one of Claims 1-4 0, wherein get rid of benzene tetramethyl amide gellant.

42. down-hole liquids according to any one of Claims 1-4 1, wherein benzene tetramethyl amide gellant has following general formula:

43. down-hole liquid according to claim 42, wherein R ₅, R ₆, R ₇and R ₈in be eachly respectively hydrogen, and one or more R ₁, R ₂, R ₃and R ₄in each be alkyl group.

44. down-hole liquid according to claim 43, wherein R ₁, R ₂, R ₃and R ₄in be eachly respectively alkyl group.

45. down-hole liquid according to claim 44, wherein R ₁=R ₂=R ₃=R ₄.

46. down-hole liquid according to claim 45, wherein R ₁, R ₂, R ₃and R ₄in each there are at least 6 carbon atoms.

47. down-hole liquids according to any one of claim 44 to 45, wherein each alkyl group has 6-24 carbon atom.

48. down-hole liquids according to claim 47, wherein each alkyl group has 6-10 carbon atom.

49. down-hole liquids according to any one of claim 43 to 48, wherein each alkyl group is one or more straight chain group, branched group or cyclic group.

50. down-hole liquids according to claim 49, wherein each alkyl group is straight chain group.

51. down-hole liquid according to claim 50, wherein R ₅, R ₆, R ₇and R ₈in each be hydrogen respectively, and R ₁, R ₂, R ₃and R ₄in each be the linear alkyl groups with 6-10 carbon atom respectively.

52. down-hole liquid according to claim 51, wherein R ₁, R ₂, R ₃and R ₄there are 6 carbon atoms.

53. down-hole liquids according to any one of claim 1 to 52, wherein base fluid comprises hydrocarbon compound.

54. down-hole liquids according to claim 53, wherein hydrocarbon compound has 3-8 carbon atom.

55. down-hole liquids according to any one of claim 1 to 54, also comprise gel breaker.

56. down-hole liquids according to claim 55, wherein said gel breaker comprises one or more bromide salt, chloride salt, organic salt and amine salt further.

57. down-hole liquids according to any one of claim 55 to 56, wherein said gel breaker comprises one or more ethanol or alkoxide.

58. down-hole liquids according to claim 57, ethanol described in wherein one or more or alkoxide have 2 or multiple carbon atom.

59. down-hole liquids according to claim 58, are wherein provided with alkoxide and alkoxide comprises aluminum isopropylate.

60. down-hole liquids according to any one of claim 55 to 59, wherein gel breaker is that water activates gel breaker and down-hole liquid comprises hydrate.

61. down-hole liquids according to any one of claim 55 to 60, wherein gel breaker comprises coating layer further.

62. down-hole liquids according to claim 61, wherein said coating layer comprises wax further.

63. 1 kinds of methods, comprise and the down-hole liquid according to any one of claim 1 to 62 are used as wellbore fluid.

65. 1 kinds of methods, comprise and the down-hole liquid according to any one of claim 1 to 63 are used as down-the hole treatment fluid.

66. for the method by down-hole liquid according to any one of claim 1 to 65 being prepared by base fluid, jelling agent, gel enhancing agent combination.

67. 1 kinds of down-hole liquids, it comprises base fluid, jelling agent and gel breaker, wherein jelling agent has the aromatic proton of one or more aromatic nucleus, described jelling agent has the two or more acid amides branches around aromatic proton distribution, and each of two or more acid amides branch has one or more organic group.

68. down-hole liquids according to claim 67, wherein said gel breaker comprises aromatic carboxylic acid.

69. down-hole liquids according to claim 68, wherein said gel breaker comprise in Ibuprofen BP/EP and phenylpropionic acid one or more.

70. down-hole liquids according to any one of claim 68 to 69, wherein said gel breaker comprise in diphenyl acetic acid, phenylformic acid and toluylic acid one or more.

71. down-hole liquids according to any one of claim 68 to 70, also comprise cation complexing agents, wherein aromatic carboxylic acid is salt.

72. according to the down-hole liquid described in claim 71, and wherein said aromatic carboxylic acid comprises ibuprofen salt, and cation complexing agents comprises citric acid.

73. down-hole liquids according to any one of claim 67 to 72, wherein said jelling agent forms hydrogen bond structure by the intermolecular hydrogen bonding between the acid amides branch of adjacent gellant molecules, and hydrogen bond between gel breaker saboteur wherein.

74. according to the down-hole liquid described in claim 73, and wherein said described gel breaker is the hydrogen bonding agent forming hydrogen bond with the acid amides branch of jelling agent, described hydrogen bond than adjacent gellant molecules acid amides branch between intermolecular hydrogen bonding stronger.

75. down-hole liquids according to claim 1 to 62 and 67 to 74 any one, wherein hydrocarbon compound comprises liquefied petroleum gas (LPG).