CN106957641A

CN106957641A - A kind of Water-In-Oil association type acidifying concentration thickening agent and preparation method thereof

Info

Publication number: CN106957641A
Application number: CN201710193249.2A
Authority: CN
Inventors: 郭拥军; 杨雪杉
Original assignee: SICHUAN GUANGYA POLYMER CHEMICAL CO Ltd
Current assignee: SICHUAN GUANGYA POLYMER CHEMICAL CO Ltd
Priority date: 2017-03-28
Filing date: 2017-03-28
Publication date: 2017-07-18

Abstract

The invention provides a kind of Water-In-Oil association type acidifying concentration thickening agent, include the component of following mass percent：20wt%~50wt% decentralized medium, the decentralized medium be and the mutual exclusive organic solvent of water；18wt%~45wt% dispersed phase, the dispersed phase is water；20wt%~40wt% hydrophobic associated polymer gelling agent for acid fluid；2.5wt%~6wt% compound emulsifying agent, the compound emulsifying agent for the emulsifying agent compounding that the compound emulsifying agent is the emulsifying agent that HLB value is 3~7 and HLB value is 8~10；Above-mentioned each component content sum is 100wt%.Concentration thickening agent stabilization time prepared by the present invention is more than 120d, and dissolution time is less than 4min, and the viscous acid performance that the concentration thickening agent prepared by the present invention is prepared is better than the viscous acid performance directly prepared by correspondence gelling agent for acid fluid dry powder.

Description

A kind of Water-In-Oil association type acidifying concentration thickening agent and preparation method thereof

Technical field

The invention belongs to petroleum technology field, and in particular to a kind of Water-In-Oil association type acidifying concentration thickening agent and its preparation Method.

Background technology

As Low permeable oil and gas reservoirs are constantly developed, acid stimulation technology turns into the important measures of frscturing.Acidifying That one kind makes that Oil/gas Well is stable, volume increase, water injection well is surely noted, the effective ways of augmented injection, be currently by oil gas well into stratum A kind of (or several) acid solution of injection or acid mixed solution, occur chemistry anti-using the part mineral in the H+ and stratum in acid solution Should, the wall rock cement of hole or crack in corrosion reservoir removes producing well injection well (water to improve in-place permeability Well) pollution near shaft bottom, the permeability of renwing stratum, so as to well during releasing drilling well, completion, well workover and augmented injection etc. The eye injury that nearby stratum is caused, dredges fluid neuron network passage, reaches the purpose recovered and improve oil gas well capacity, conventional Acid liquid viscosity is low, and penetration depth is small, and filtration rate is fast, and pitting corrosion is caused around pit shaft, and acidifying transformation does not reach the effect of anticipation.

Viscous acid can effectively overcome the shortcoming of above-mentioned conventional acidulation technology.Viscous acid refer in acid add thickening agent (or Claim gelling agent), increase acid liquid viscosity, effectively hydrogen ion diffusion rate in control acid solution, release the pollution in remote well area, link up Oil gas flow-guiding channel, improves oil and gas production.

The key of viscous acid is thickening agent, the main natural polymerses of viscous acid thickening agent of current industrial application and Polyacrylamide synthetic polymer, it exists following not enough：Heatproof, salt resistance, anti-shear performance are poor, and tackifying is poor, dissolubility Preparation aspect needs to spend the more time difference at the scene, improves construction cost.Therefore, researcher proposes on this basis Hydrophobic associated polymer gelling agent for acid fluid.Hydrophobically associating polymers (Hydrophobically Associating Water-Soluble Polymers, HAWSP), refer to carry a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain Water-soluble polymer.In aqueous, HAWSP concentration is higher than after critical association concentration, and macromolecular chain passes through heat resistance and salt tolerance Aggregation, solution viscosity significantly raises, and the system and possesses excellent thickening, heatproof, salt resistance, anti-shear performance.

The application performance of the above-mentioned hydrophobic associated polymer thickening technic acid being related to gradually has tended to be ripe, its site operation Technique is mainly using " matching somebody with somebody marginal not in side ", i.e., continuous allocation process technology is exactly application at the scene directly by thickening agent dry powder, addition Agent is mixed to form corresponding viscous acid working solution with acid.But current this continuous allocation process technology, some shortcomings are still suffered from, Such as it is acidified labor intensity when thickening agent is prepared at the scene big, dry powder (thickening agent) feeds intake with dust greatly, mixes uneven, easily formed Powder flake, produces local frozen glue caking, dissolves insufficient, influences solution property, and involved liquid, equipment and instrument are big Increase construction cost and difficulty of construction greatly.

The content of the invention

In view of this, the technical problem to be solved in the present invention is to provide a kind of Water-In-Oil association type acidifying concentration thickening agent And preparation method thereof, the Water-In-Oil association type acidifying concentration thickening agent that the present invention is provided can effectively solve the dissolving in continuous mixture Sex chromosome mosaicism, it has good performance, reduces technology difficulty and production cost, while reducing environmental pollution.

The invention provides a kind of Water-In-Oil association type acidifying concentration thickening agent, include the component of following mass percent：

20wt%~50wt% decentralized medium, the decentralized medium be and the mutual exclusive organic solvent of water；

18wt%~45wt% dispersed phase, the dispersed phase is water；

20wt%~40wt% hydrophobic associated polymer gelling agent for acid fluid；

2.5wt%~6wt% compound emulsifying agent, the compound emulsifying agent is the emulsifying agent and HLB value that HLB value is 3~7 For the compound emulsifying agent of 8~10 emulsifying agent compounding；

Above-mentioned each component content sum is 100wt%.

It is preferred that, the mass ratio for the emulsifying agent that the emulsifying agent that the HLB value is 3~7 is 8~10 with HLB value is (4~6): (1~3).

It is preferred that, the HLB value is selected from propylene glycol monostearate BPMS, propane diols mono laurate for 3~7 emulsifying agent It is the double stearate DEGDS of ester BPML, diethylene glycol monostearate DEGMS, diethylene glycol, polyglycerol polyricinoleate PGPR, poly- Ethylene glycol dioleic acid ester PEG400DO, polyoxyethylene oleic acid ester A-103, methyl glycol fatty acid ester PGMS, oleic acid diethyl amide ODEA, paregal O O-3, Emulsifier EL-60 EL-10, Emulsifier EL-60 EL-12, propylene glycol block polyether L62 and One or more in three Risorex PGIS 22s；

The HLB value is selected from AEO AEO-3, AEO for 8~10 emulsifying agent It is AEO-4, Emulsifier EL-60 EL-20, Emulsifier EL-60 HEL20, diacetyl tartarate list double glyceride DATEM, hard Resin acid polyoxyethylene ester SG-6, laurate APEO LAE-4, paregal O O-5, polyoxyethylene oleic acid ester A-105 and poly- One or more in ethylene glycol bilaurate PEG400DL.

It is preferred that, the compound emulsifying agent is selected from the compound of propylene glycol monostearate BPMS and paregal O O-5 formation Emulsifying agent, PGML BPML and Emulsifier EL-60 EL-20 formation compound emulsifying agent, the double oil of polyethylene glycol The compound emulsifying agent of acid esters PEG400DO and AEO AEO-3 formation, diethylene glycol monostearate DEGMS with Compound emulsifying agent, polyoxyethylene oleic acid ester A-103 and the diacetyl tartarate list that laurate APEO LAE-4 is formed are double sweet The double stearate DEGDS and polyoxyethylene oleic acid ester A-105 formation of the compound emulsifying agent of grease DATEM formation, diethylene glycol Compound emulsifying agent, polyglycerol polyricinoleate PGPR and polyethylene glycol bilaurate PEG400DL formation compound emulsifying agent, third The compound emulsifying agent of diol block polyethers L62 and AEO AEO-3 formation, Emulsifier EL-60 EL-10 with Compound emulsifying agent, methyl glycol fatty acid ester PGMS and the Emulsifier EL-60 HEL20 of AEO AEO-4 formation The compound emulsifying agent of formation, paregal O O-3 and polyoxyethylene stearic acid ester SG-6 formation compound emulsifying agent, oleic acid diethanol The compound emulsifying agent or three Risorex PGIS 22s and AEO of acid amides ODEA and paregal O O-5 formation The compound emulsifying agent of AEO-3 formation.

It is preferred that, the hydrophobic associated polymer gelling agent for acid fluid has molecular formula shown in formula (I)：

Wherein, A is the monomeric unit of hydrophilic monomer, and the hydrophilic monomer is acrylamide, Methacrylamide, the tertiary fourths of N- Any one or more in base acrylamide and NIPA；

B is the monomeric unit of cation hydrophobic monomer, and the cation hydrophobic monomer is acryloyloxyalkyl quaternary ammonium salt, long Alkyl quaternary ammonium salts unsaturated monomer, polyoxyethylene base dibrominated tetramethylethylenediamine, diallyl quaternary ammonium and (4- acryloyls Amido) any one or more in phenylalkyl ditallowdimethyl ammonium bromide；

C be function monomer monomeric unit, the function monomer be 2- acrylamide-2-methylpro panesulfonic acids or its salt, Any one or more in vinyl sulfonic acid or its salt, styrene sulfonic acid or its salt and NVP；

X, y, z is the mole percent of monomeric unit in hydrophobic associated polymer；Y be 0.1%~20%, z be 0~ 30%；X, y, z summation is 1.

It is preferred that, the described and one kind of the mutual exclusive organic solvent of water in diesel oil, kerosene, atoleine and white oil Or it is a variety of.

Present invention also offers a kind of preparation method of above-mentioned Water-In-Oil association type acidifying concentration thickening agent, its feature exists In comprising the following steps：

A) dispersed phase, decentralized medium and compound emulsifying agent are mixed, water-in-oil emulsion is obtained；

B hydrophobic associated polymer gelling agent for acid fluid) is added into the water-in-oil emulsion, mixes, obtains Water-In-Oil Association type acidifying concentration thickening agent.

It is preferred that, step A) in, the temperature of the mixing is 35~70 DEG C, and the rotating speed of the mixing is 300 ~800rmp, the time of the mixing is 20~60min.

It is preferred that, step B) in, the mixing temperature is 35~70 DEG C, the rotating speed of the mixing for 600~ 2000rmp, the mixing time is 40~120min.

Present invention also offers a kind of gelling agent for acid fluid, including above-mentioned Water-In-Oil association type acidifying concentration thickening agent or on State the Water-In-Oil association type acidifying concentration thickening agent of preparation method preparation.

Compared with prior art, the invention provides a kind of Water-In-Oil association type acidifying concentration thickening agent, including following matter Measure the component of percentage：20wt%~50wt% decentralized medium, the decentralized medium be and the mutual exclusive organic solvent of water； 18wt%~45wt% dispersed phase, the dispersed phase is water；20wt%~40wt% hydrophobic associated polymer acid solution thickening Agent；2.5wt%~6wt% compound emulsifying agent, the compound emulsifying agent be the emulsifying agent that HLB value is 3~7 and HLB value be 8~ The compound emulsifying agent of 10 emulsifying agent compounding；Above-mentioned each component content sum is 100wt%.

The emulsifying agent (surfactant) contained in the Water-In-Oil association type acidifying concentration thickening agent that the present invention is provided is two The compound emulsifying agent of single emulsifier compounding is planted, it can produce positive coorperativity with association polymer gelling agent for acid fluid in the solution and make With, and then increase system viscosity, improve system solution performance, enhancing viscoplasticity etc..Meanwhile, by concentration thickening agent prepared it is thick Change association polymer in acid system solution can be with that can make Interpolymer Association dynamic physical cross-linked network after applying surface activating agent compounding Network intensity is further enhanced, and strengthens the performance such as the heatproof for being thickened acid system, salt tolerant, anti-shearing.In addition, of the invention by continuous injection allocation Technology is changed to semicontinuous allocation process technology, that is, prepares in base the hydrophobic associated polymer thickening agent of high concentration Slurry, i.e. Water-In-Oil association type acidifying concentration thickening agent, and in job site by blender, the method is simple to operate, thickening agent Dissolution time substantially shortens, and solubility property is significantly improved, and does not produce flake powder, improves the performance of gelling agent for acid fluid, compared with Big degree reduces technology difficulty and production cost, while reducing environmental pollution.

Embodiment

18wt%~45wt% dispersed phase, the dispersed phase is water；

20wt%~40wt% hydrophobic associated polymer gelling agent for acid fluid；

2.5wt%~6wt% compound emulsifying agent, the compound emulsifying agent includes the emulsifying agent and HLB that HLB value is 3~7 It is worth the compound emulsifying agent of the emulsifying agent compounding for 8~10；

Above-mentioned each component content sum is 100wt%.

The Water-In-Oil association type acidifying concentration thickening agent that the present invention is provided includes decentralized medium, the addition of the decentralized medium Measure as 20wt%~50wt%, more preferably preferably 25wt%~45wt%, 28wt%~42wt%.The mutual not phase with water The organic solvent of appearance is preferably the one or more in diesel oil, kerosene, atoleine and white oil, more preferably diesel oil, kerosene, liquid Body paraffin or white oil.

The Water-In-Oil association type acidifying concentration thickening agent that the present invention is provided also includes dispersed phase, and the dispersed phase is water, institute The addition for stating dispersed phase is 18wt%~45wt%, more preferably preferably 20wt%~40wt%, 25wt%~35wt%.

The Water-In-Oil association type acidifying concentration thickening agent that the present invention is provided also includes hydrophobic associated polymer gelling agent for acid fluid, The hydrophobic associated polymer gelling agent for acid fluid has molecular formula shown in formula (I)：

In the present invention, in the acryloyloxyalkyl quaternary ammonium salt, atomic number of alkyl carbon is preferably 4~20, and more preferably 6 ~15；

In the long chain alkyl ammonium salt unsaturated monomer, chain alkyl carbon number is preferably 4~20, and more preferably 12 ~18；

In the polyoxyethylene base dibrominated tetramethylethylenediamine, atomic number of alkyl carbon is preferably 8~20, more preferably 8~ 10；

The diallyl quaternary ammonium is preferably dimethyl diallyl ammonium chloride；

In (4- acrylamidos) the phenylalkyl ditallowdimethyl ammonium bromide, atomic number of alkyl carbon is preferably 4~20, more excellent Elect 4~8 as.

In certain specific embodiments of the invention, the hydrophobic associated polymer gelling agent for acid fluid be acrylamide/ Acryloyl-oxy myristyl quaternary ammonium salt/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, acrylamide/acryloyl-oxy ten Dialkyl quats salt/vinyl-sulfonate copolymer, acrylamide/acryloyl-oxy cetyl quaternary ammonium salt/styrene sulfonic acid Salt copolymer, acrylamide/acryloyl-oxy nonane based quaternary ammonium salt/NVP copolymer, acrylamide/ten Dialkyl dimethyl allyl ammonium chloride/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, acrylamide/myristyl Dimethyl-allyl ammonium bromide/vinyl-sulfonate copolymer, acrylamide/hexadecyldimethyl benzyl ammonium allylic bromination ammonium/benzene Vinyl-sulfonate copolymer, acrylamide/solution property/NVP are common Polymers, acrylamide/pentyl pi-allyl dibrominated tetramethylethylenediamine/2- acrylamide-2-methylpro panesulfonic acid salt copolymerization Thing, acrylamide/octyl pi-allyl dibrominated tetramethylethylenediamine/vinyl-sulfonate copolymer, acrylamide/nonyl Pi-allyl dibrominated tetramethylethylenediamine/styrene sulfonic acid salt copolymer, acrylamide/decyl pi-allyl dibrominated tetramethyl Base ethylenediamine/NVP copolymer, acrylamide/dimethyl diallyl ammonium chloride/2- acrylamides Base -2- methyl propane sulfonic acids salt copolymer, acrylamide/dimethyl diallyl ammonium chloride/vinyl-sulfonate copolymer, propylene Acid amides/dimethyl diallyl ammonium chloride/styrene sulfonic acid salt copolymer, acrylamide/dimethyl diallyl ammonium chloride/ NVP copolymer, acrylamide/(4- acrylamidos) phenyl pentane base ditallowdimethyl ammonium bromide/2- third Acrylamide base -2- methyl propane sulfonic acids salt copolymer, acrylamide/(4- acrylamidos) hexane phenyl base ditallowdimethyl ammonium bromide/ Vinyl-sulfonate copolymer, acrylamide/(4- acrylamidos) phenylheptan base ditallowdimethyl ammonium bromide/styrene sulfonic acid Salt copolymer, acrylamide/(4- acrylamidos) phenyl-octane base ditallowdimethyl ammonium bromide/NVP are common Polymers, Methacrylamide/acryloyl-oxy dodecyl quaternary ammonium salt/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, first Base acrylamide/dodecyldimethylamine base allylic bromination ammonium/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, methyl Acrylamide/nonyl pi-allyl dibrominated tetramethylethylenediamine/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, first Base acrylamide/dimethyl diallyl ammonium chloride/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, methacryl Amine/(4- acrylamidos) hexane phenyl base ditallowdimethyl ammonium bromide/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, N- N-tert-butyl acrylamide/acryloyl-oxy myristyl quaternary ammonium salt/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, uncle N- Butylacrylamide/hexadecyldimethyl benzyl ammonium allylic bromination ammonium/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, N- N-tert-butyl acrylamide/octyl pi-allyl dibrominated tetramethylethylenediamine/2- acrylamide-2-methylpro panesulfonic acid salt copolymerization Thing, N tert butyl acrylamide/dimethyl diallyl ammonium chloride/2- acrylamide-2-methylpro panesulfonic acids salt copolymer, N- N-tert-butyl acrylamide/(4- acrylamidos) phenyl-octane base ditallowdimethyl ammonium bromide/2- acrylamide-2-methylpro panesulfonic acids Salt copolymer, NIPA/acryloyl-oxy dodecyl quaternary ammonium salt/2- acrylamide-2-methylpro panesulfonic acid salt Copolymer, NIPA/octadecyldimethyl allylic bromination ammonium/2- acrylamide-2-methylpro panesulfonic acids Salt copolymer, NIPA/nonyl pi-allyl dibrominated tetramethylethylenediamine/2- acrylamido -2- methyl Propane sulfonic acid salt copolymer, acrylamide/dimethyl diallyl ammonium chloride diallyl quaternary ammonium/2- acrylamido -2- first Base propane sulfonic acid salt copolymer, NIPA/(4- acrylamidos) phenyl-octane base ditallowdimethyl ammonium bromide/2- propylene Amide groups -2- methyl propane sulfonic acids salt copolymer, Methacrylamide/acryloyl-oxy myristyl quaternary ammonium salt/vinylsulfonate Copolymer, N tert butyl acrylamide/acryloyl-oxy dodecyl quaternary ammonium salt/styrene sulfonic acid salt copolymer, N- isopropyls Acrylamide/acryloyl-oxy cetyl quaternary ammonium salt/NVP copolymer or Methacrylamide/diformazan Base diallyl ammonium chloride/styrene sulfonic acid salt copolymer.

In the present invention, the hydrophobic associated polymer gelling agent for acid fluid dry powder uses 100 mesh sieve net filtrations.

The addition of the hydrophobic associated polymer gelling agent for acid fluid be 20wt%~40wt%, preferably 25wt%~ 35wt%, more preferably 27wt%~33wt%.

The Water-In-Oil association type acidifying concentration thickening agent that the present invention is provided also includes compound emulsifying agent, the compound emulsifying agent Addition be 2.5wt%~6wt%, more preferably preferably 3.0wt%~5wt%, 3.2wt%~4.5wt%.

The Composite Milk for the emulsifying agent compounding that the compound emulsifying agent is the emulsifying agent that HLB value is 3~7 and HLB value is 8~10 Agent, the mass ratio for the emulsifying agent that the emulsifying agent that the HLB value is 3~7 is 8~10 with HLB value is (4~6):(1~3), it is excellent Elect as (1.5~5.5)：(1.5~2.5).

The HLB value for 3~7 emulsifying agent be selected from propylene glycol monostearate BPMS, PGML BPML, The double stearate DEGDS of diethylene glycol monostearate DEGMS, diethylene glycol, polyglycerol polyricinoleate PGPR, polyethylene glycol are double It is oleate PEG400DO, polyoxyethylene oleic acid ester A-103, methyl glycol fatty acid ester PGMS, oleic acid diethyl amide ODEA, average Plus O O-3, Emulsifier EL-60 EL-10, Emulsifier EL-60 EL-12, propylene glycol block polyether L62 and three polyglycereol two One or more in isostearate, it is preferred that the HLB value is selected from propylene glycol monostearate for 3~7 emulsifying agent It is the double stearate DEGDS of BPMS, PGML BPML, diethylene glycol monostearate DEGMS, diethylene glycol, poly- Glycerine polyricinoleate PGPR, polyethylene glycol dioleic acid ester PEG400DO, polyoxyethylene oleic acid ester A-103, methyl glycol fatty acid ester PGMS, oleic acid diethyl amide ODEA, paregal O O-3, Emulsifier EL-60 EL-10, Emulsifier EL-60 EL-12, One or more in propylene glycol block polyether L62 and three Risorex PGIS 22s；

The HLB value is selected from AEO AEO-3, AEO for 8~10 emulsifying agent It is AEO-4, Emulsifier EL-60 EL-20, Emulsifier EL-60 HEL20, diacetyl tartarate list double glyceride DATEM, hard Resin acid polyoxyethylene ester SG-6, laurate APEO LAE-4, paregal O O-5, polyoxyethylene oleic acid ester A-105 and poly- One or more in ethylene glycol bilaurate PEG400DL, it is preferred that the HLB value is selected from fat for 8~10 emulsifying agent Fat alcohol APEO AEO-3, AEO AEO-4, Emulsifier EL-60 EL-20, Emulsifier EL-60 HEL20, diacetyl tartarate list double glyceride DATEM, polyoxyethylene stearic acid ester SG-6, laurate APEO LAE-4, One or more in paregal O O-5, polyoxyethylene oleic acid ester A-105 and polyethylene glycol bilaurate PEG400DL.

In certain specific embodiments of the invention, the compound emulsifying agent be selected from propylene glycol monostearate BPMS with The compound emulsifying agent of paregal O O-5 formation；In other embodiments of the present invention, the compound emulsifying agent is third The compound emulsifying agent of glycol monolaurate BPML and Emulsifier EL-60 EL-20 formation；Other in the present invention are specific In embodiment, the compound emulsifying agent is polyethylene glycol dioleic acid ester PEG400DO and AEO AEO-3 shapes Into compound emulsifying agent；In other embodiments of the present invention, the compound emulsifying agent is that diethylene glycol list is stearic The compound emulsifying agent of acid esters DEGMS and laurate APEO LAE-4 formation；In other embodiments of the present invention In, the compound emulsifying agent is the compound of polyoxyethylene oleic acid ester A-103 and diacetyl tartarate list double glyceride DATEM formation Emulsifying agent；In other embodiments of the present invention, the compound emulsifying agent is the double stearate DEGDS of diethylene glycol With the compound emulsifying agent of polyoxyethylene oleic acid ester A-105 formation；It is described compound in other embodiments of the present invention Emulsifying agent is the compound emulsifying agent of polyglycerol polyricinoleate PGPR and polyethylene glycol bilaurate PEG400DL formation, in this hair In other bright embodiments, the compound emulsifying agent is propylene glycol block polyether L62 and AEO The compound emulsifying agent of AEO-3 formation；In other embodiments of the present invention, the compound emulsifying agent is polyoxyethylene The compound emulsifying agent of castor oil EL-10 and AEO AEO-4 formation；In other specific embodiment parties of the present invention In formula, the compound emulsifying agent is the compound emulsifying agent of methyl glycol fatty acid ester PGMS and Emulsifier EL-60 HEL20 formation； In other embodiments of the present invention, the compound emulsifying agent is paregal O O-3 and polyoxyethylene stearic acid ester The compound emulsifying agent of SG-6 formation；In other embodiments of the present invention, the compound emulsifying agent is oleic acid diethyl The compound emulsifying agent of alkylolamides ODEA and paregal O O-5 formation；It is described multiple in other embodiments of the present invention Co-emulsifier is three Risorex PGIS 22s and the compound emulsifying agent of AEO AEO-3 formation.

The complex emulsifier that the present invention is provided can strengthen system stability, and wherein HLB value is larger in compound emulsifying agent Reinforced partly its affinity between water, and the compound use of two kinds of emulsifying agents, the emulsifying agent point in emulsion system Son is alternately adsorbed on the surface of emulsion particle, is also equivalent between the emulsifying agent of nonionic and be embedded in nonionic Emulsifier molecules, this just greatly strengthen the firmness that emulsifying agent is adsorbed on emulsion particle, along with non-ionic surface active Agent has the effect of protection emulsion particle in itself, so as to further increase the stability of emulsion system.

Present invention also offers a kind of preparation method of above-mentioned Water-In-Oil association type acidifying concentration thickening agent, including following step Suddenly：

The present invention first mixes dispersed phase, decentralized medium and compound emulsifying agent, obtains water-in-oil emulsion, mixing is stirred The temperature mixed is 35~70 DEG C, more preferably preferably 40~60 DEG C, 45~55 DEG C；The rotating speed of the mixing be 300~ 800rmp, preferably 300~600rmp；The time of the mixing is 20~40min.

Obtain after water-in-oil emulsion, hydrophobic associated polymer gelling agent for acid fluid is added into the water-in-oil emulsion, it is described It is 35~70 DEG C, more preferably preferably 40~60 DEG C, 45~55 DEG C to mix temperature；The rotating speed of the mixing is 600~2000rmp, preferably 800~1500rmp；The mixing time be 40~120min, preferably 60~ 100min。

The emulsifying agent (surfactant) contained in the Water-In-Oil association acidifying concentration thickening agent that the present invention is provided is two kinds The compound emulsifying agent of single emulsifier compounding, it can produce positive coorperativity with water-soluble association polymer thickening agent in the solution and make With, and then increase system viscosity, improve system solution performance, enhancing viscoplasticity etc..Meanwhile, by concentration thickening agent prepared it is thick Change association polymer in acid system solution can be with that can make Interpolymer Association dynamic physical cross-linked network after applying surface activating agent compounding Network intensity is further enhanced, and strengthens the performance such as the heatproof for being thickened acid system, salt tolerant, anti-shearing.In addition, of the invention by continuous injection allocation Technology is changed to semicontinuous allocation process technology, that is, prepares in base the hydrophobic associated polymer thickening agent of high concentration Slurry, i.e. Water-In-Oil association type acidifying concentration thickening agent, and in job site by blender, the method is simple to operate, thickening agent Dissolution time substantially shortens, and solubility property is significantly improved, and does not produce flake powder, improves the performance of gelling agent for acid fluid, compared with Big degree reduces technology difficulty and production cost, while reducing environmental pollution.

For a further understanding of the present invention, the Water-In-Oil association type that the present invention is provided is acidified with reference to embodiment and concentrated Thickening agent and preparation method thereof is illustrated, and protection scope of the present invention is not limited by the following examples.

Embodiment 1

Preparation (the compound emulsifying agent of Water-In-Oil (W/O) association type acidifying concentration thickening agent：Propylene glycol monostearate BPMS + paregal O O-5)

(1) a kind of W/O association types acidifying concentration thickening agent, includes the component of following mass percent：

0# diesel oil 38.22%, water 38.22%, hydrophobic associated polymer gelling agent for acid fluid 20%, propylene glycol monostearate BPMS 2.85%, paregal O O-5 0.71%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/acryloyl-oxy myristyl quaternary ammonium salt/2- third Acrylamide base -2- methyl propane sulfonic acids salt copolymer, described compound emulsifying agent is BPMS and O-5 (ratios 4:1), preparation process It is as follows：

At a temperature of 40 DEG C, it is 5 to control profit mass ratio:5, by 382.2g diesel oil, 382.2g water, 28.5g BPMS, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.1g O-5,600rmp rotating speed, is eventually adding 200g Hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms the oil that uniform and stable mass fraction is 20% Bag water association type acidifying concentration thickening agent.

(2) a kind of W/O association types acidifying concentration thickening agent, includes the component of following mass percent：

Kerosene 37.35%, water 30.57%, hydrophobic associated polymer gelling agent for acid fluid 28%, propylene glycol monostearate BPMS 3.06%, paregal O O-5 1.02%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/acryloyl-oxy dodecyl quaternary ammonium salt/ethene Base co-polymer of sulfonate, described compound emulsifying agent is BPMS and O-5 (ratios 3:1), preparation process is as follows：

At a temperature of 50 DEG C, it is 5.5 to control profit mass ratio:4.5, by 373.5g kerosene, 305.7g water, 30.6g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of BPMS, 10.2g O-5,600rmp rotating speed, finally adds Enter 280g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

(3) a kind of W/O association types acidifying concentration thickening agent, includes the component of following mass percent：

0# atoleines 33.25%, water 22.17%, hydrophobic associated polymer gelling agent for acid fluid 40%, propane diols list is stearic Acid esters BPMS 3.27%, paregal O O-5 1.31%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/acryloyl-oxy cetyl quaternary ammonium salt/benzene second Olefin sulfonic acid salt copolymer, described compound emulsifying agent is BPMS and O-5 (ratios 5:2), preparation process is as follows：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 332.5g atoleines, 221.7g water, 32.7g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of BPMS, 13.1g O-5,600rmp rotating speed, finally adds Enter 400g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1500rmp forms uniform and stable mass fraction and is 40% Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 2

(compound emulsifying agent is PGML for the preparation of Water-In-Oil (W/O) association type acidifying concentration thickening agent BPML+ Emulsifier EL-60 EL-20)

0# diesel oil 42.86%, water 28.57%, hydrophobic associated polymer gelling agent for acid fluid 25%, PGML BPML2.14%, Emulsifier EL-60 EL-20 1.43%；

Described hydrophobic associated polymer gelling agent for acid fluid be acrylamide/acryloyl-oxy nonyl quaternary ammonium salt/N- vinyl- 2-Pyrrolidone copolymer, described compound emulsifying agent is BPML and EL-20 (ratios 3:2), preparation process is as follows：

At a temperature of 50 DEG C, it is 6 to control profit mass ratio:4, by 428.6g diesel oil, 285.7g water, 21.4g BPML, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 14.3g EL-20,600rmp rotating speed, is eventually adding 250g hydrophobic associated polymer gelling agent for acid fluid, it is 25% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

White oil 44.15%, water 23.77%, hydrophobic associated polymer gelling agent for acid fluid 28%, PGML BPML2.38%, Emulsifier EL-60 EL-20 1.70%；

Described hydrophobic associated polymer gelling agent for acid fluid be acrylamide/dodecylallyldimethylammonium chloride/ 2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is BPML and EL-20 (ratios 7:5), prepare Step is as follows：

At a temperature of 50 DEG C, it is 6.5 to control profit mass ratio:3.5, by 441.5g white oils, 237.7g water, 23.8g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of BPML, 17g EL-20,600rmp rotating speed, finally adds Enter 280g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1200rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

Kerosene 45.79%, water 19.63%, hydrophobic associated polymer gelling agent for acid fluid 30%, PGML BPML2.62%, Emulsifier EL-60 EL-20 1.96%；

Described hydrophobic associated polymer gelling agent for acid fluid be acrylamide/dodecyldimethylamine base allylic bromination ammonium/ Vinyl-sulfonate copolymer, described compound emulsifying agent is BPML and EL-20 (ratios 4:3), preparation process is as follows：

At a temperature of 60 DEG C, it is 7 to control profit mass ratio:3, by 457.9g kerosene, 196.3g water, 26.2g BPML, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 19.6g EL-20,600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1500rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 3

Preparation (the polyethylene glycol dioleic acid ester PEG400DO+ fatty alcohols of Water-In-Oil (W/O) association type acidifying concentration thickening agent APEO AEO-3)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, polyethylene glycol dioleic acid ester PEG400DO 2.16%, AEO AEO-3 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid be acrylamide/hexadecyldimethyl benzyl ammonium allylic bromination ammonium/ Styrene sulfonic acid salt copolymer, described compound emulsifying agent is PEG400DO and AEO-3 (ratios 3:1), preparation process is as follows：

At a temperature of 50 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of PEG400DO, 7.2g AEO-3,600rmp rotating speed, 250g hydrophobic associated polymer gelling agent for acid fluid is eventually adding, the high speed shear through 1000rmp forms uniform and stable quality point Number concentrates thickening agent for 25% Water-In-Oil association type acidifying.

Atoleine 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, the double oleic acid of polyethylene glycol Ester PEG400DO 2.43%, AEO AEO-3 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid be acrylamide/solution property/ NVP copolymer, described compound emulsifying agent is PEG400DO and AEO-3 (ratios 7:3), preparation process It is as follows：

At a temperature of 55 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g atoleines, 308.4g water, 24.3g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of PEG400DO, 10.4g AEO-3,600rmp rotating speed, 280g hydrophobic associated polymer gelling agent for acid fluid is eventually adding, the high speed shear through 1000rmp forms uniform and stable quality point Number concentrates thickening agent for 28% Water-In-Oil association type acidifying.

White oil 36.62%, water 24.42%, hydrophobic associated polymer gelling agent for acid fluid 35%, polyethylene glycol dioleic acid ester PEG400DO 2.64%, AEO AEO-3 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/amyl group pi-allyl dibrominated tetramethyl second two Amine/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is PEG400DO and AEO-3 (ratios 2: 1), preparation process is as follows：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 366.2g white oils, 244.2g water, 26.4g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsification of PEG400DO, 13.2gAEO-3,600rmp rotating speed, 350g hydrophobic associated polymer gelling agent for acid fluid is eventually adding, the high speed shear through 1000rmp forms uniform and stable quality point Number concentrates thickening agent for 35% Water-In-Oil association type acidifying.

Embodiment 4

Preparation (the diethylene glycol monostearate DEGMS+ laurate of Water-In-Oil (W/O) association type acidifying concentration thickening agent APEO LAE-4)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, diethylene glycol monostearate Ester DEGMS 2.16%, laurate APEO LAE-4 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/octyl group pi-allyl dibrominated tetramethyl second two Amine/vinyl-sulfonate copolymer, described compound emulsifying agent is DEGMS and LAE-4 (ratios 3:1), preparation process is as follows：

At a temperature of 55 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g DEGMS, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.2g LAE-4,600rmprmp rotating speed, finally adds Enter 250g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmprmp forms uniform and stable mass fraction and is 25% Water-In-Oil association type acidifying concentration thickening agent.

0# diesel oil 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, diethylene glycol monostearate Ester DEGMS 2.43%, laurate APEO LAE-4 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/nonyl pi-allyl dibrominated tetramethyl second two Amine/styrene sulfonic acid salt copolymer, described compound emulsifying agent is DEGMS and LAE-4 (ratios 7:3), preparation process is as follows：

At a temperature of 55 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g diesel oil, 308.4g water, 24.3g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of DEGMS, 10.4g LAE-4,600rmp rotating speed, most 280g hydrophobic associated polymer gelling agent for acid fluid is added afterwards, and the high speed shear through 1000rmp forms uniform and stable mass fraction For 28% Water-In-Oil association type acidifying concentration thickening agent.

Kerosene 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, diethylene glycol monostearate DEGMS 2.64%, laurate APEO LAE-4 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/decyl pi-allyl dibrominated tetramethyl second two Amine/NVP copolymer, described compound emulsifying agent is DEGMS and LAE-4 (ratios 2:1), preparation process It is as follows：

At a temperature of 60 DEG C, it is 5.5 to control profit mass ratio:4.5, by 396.2g kerosene, 264.2g water, 26.4g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of DEGMS, 13.2g LAE-4,600rmp rotating speed, most 300g hydrophobic associated polymer gelling agent for acid fluid is added afterwards, and the high speed shear through 1000rmp forms uniform and stable mass fraction For 30% Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 5

Preparation (the polyoxyethylene oleic acid ester A-103+ diacetyl tartarics of Water-In-Oil (W/O) association type acidifying concentration thickening agent Sour list double glyceride DATEM)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, polyoxyethylene oleic acid ester A- 103 2.16%, diacetyl tartarate list double glyceride DATEM0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/dimethyl diallyl ammonium chloride/2- propylene Amide groups -2- methyl propane sulfonic acid salt copolymers, described compound emulsifying agent is A103 and DATEM (ratios 3:1), preparation process is such as Under：

At a temperature of 40 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g A103, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.2g DATEM, 600rmp rotating speed, is eventually adding 250g hydrophobic associated polymer gelling agent for acid fluid, it is 25% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

White oil 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, polyoxyethylene oleic acid ester A- 103 2.43%, diacetyl tartarate list double glyceride DATEM1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/dimethyl diallyl ammonium chloride/vinyl Co-polymer of sulfonate, described compound emulsifying agent is A103 and DATEM (ratios 7:3), preparation process is as follows：

At a temperature of 50 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g white oils, 308.4g water, 24.3g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of A103,10.4g DATEM, 600rmp rotating speed, finally 280g hydrophobic associated polymer gelling agent for acid fluid is added, the high speed shear through 1200rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

0# diesel oil 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, polyoxyethylene oleic acid ester A- 103 2.64%, diacetyl tartarate list double glyceride DATEM1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/dimethyl diallyl ammonium chloride/styrene Base co-polymer of sulfonate, described compound emulsifying agent is A103 and DATEM ((ratios 2:1), preparation process is as follows：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 396.2g diesel oil, 264.2g water, 26.4gA103, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.2g DATEM, 600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1500rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 6

Preparation (the double stearates of compound emulsifying agent diethylene glycol of Water-In-Oil (W/O) association type acidifying concentration thickening agent DEGDS+ polyoxyethylene oleic acid ester A-105)

0# diesel oil 35.72%, water 35.72%, hydrophobic associated polymer gelling agent for acid fluid 25%, the double stearic acid of diethylene glycol Ester DEGDS 2.85%, polyoxyethylene oleic acid ester A-105 0.71%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/dimethyl diallyl ammonium chloride/N- ethene Base -2-Pyrrolidone copolymer, described compound emulsifying agent is DEGDS and A-105 (ratios 4:1), preparation process is as follows：

At a temperature of 60 DEG C, it is 5 to control profit mass ratio:5, by 357.2g diesel oil, 357.2g water, 28.5g DEGDS, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.1g A-105,600rmp rotating speed, is eventually adding 250g hydrophobic associated polymer gelling agent for acid fluid, it is 25% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Kerosene 37.35%, water 30.57%, hydrophobic associated polymer gelling agent for acid fluid 28%, the double stearates of diethylene glycol DEGDS 3.06%, polyoxyethylene oleic acid ester A-105 1.02%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/(4- acrylamidos) phenylpentyl dimethyl Ammonium bromide/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is DEGDS and A-105 (ratios 3:1), preparation process is as follows：

At a temperature of 60 DEG C, it is 5.5 to control profit mass ratio:4.5, by 373.5g kerosene, 305.7g water, 30.6g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of DEGDS, 10.2g A-105,600rmp rotating speed, most 280g hydrophobic associated polymer gelling agent for acid fluid is added afterwards, and the high speed shear through 1200rmp forms uniform and stable mass fraction For 28% Water-In-Oil association type acidifying concentration thickening agent.

Atoleine 39.25%, water 26.17%, hydrophobic associated polymer gelling agent for acid fluid 30%, diethylene glycol is double stearic Acid esters DEGDS 3.27%, polyoxyethylene oleic acid ester A-105 1.31%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/(4- acrylamidos) Phenylhexyl dimethyl Ammonium bromide/vinyl-sulfonate copolymer, described compound emulsifying agent is DEGDS and A-105 (ratios 5:2), preparation process is such as Under：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 392.5g atoleines, 261.7g water, 32.7g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of DEGDS, 13.1g A-105,600rmp rotating speed, most 300g hydrophobic associated polymer gelling agent for acid fluid is added afterwards, and the high speed shear through 1500rmp forms uniform and stable mass fraction For 30% Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 7

(compound emulsifying agent polyglycerol polyricinoleate PGPR+ gathers for the preparation of Water-In-Oil (W/O) association type acidifying concentration thickening agent Ethylene glycol bilaurate PEG400DL)

Kerosene 35.72%, water 35.72%, hydrophobic associated polymer gelling agent for acid fluid 25%, polyglycerol polyricinoleate PGPR 2.85%, polyethylene glycol bilaurate PEG400DL0.71%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/(4- acrylamidos) phenylheptyl dimethyl Ammonium bromide/styrene sulfonic acid salt copolymer, described compound emulsifying agent is PGPR and PEG400DL (ratios 4:1) step, is prepared It is rapid as follows：

At a temperature of 60 DEG C, it is 5 to control profit mass ratio:5, by 357.2g kerosene, 357.2g water, 28.5g PGPR, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.1g PEG400DL, 600rmp rotating speed, finally adds Enter 250g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms uniform and stable mass fraction and is 25% Water-In-Oil association type acidifying concentration thickening agent.

0# diesel oil 37.35%, water 30.57%, hydrophobic associated polymer gelling agent for acid fluid 28%, polyglycerol polyricinoleate PGPR3.06%, polyethylene glycol bilaurate PEG400DL1.02%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/(4- acrylamidos) phenyl octyldimethyl Ammonium bromide/NVP copolymer, described compound emulsifying agent is PGPR and PEG400DL (ratios 3:1), make Standby step is as follows：

At a temperature of 60 DEG C, it is 5.5 to control profit mass ratio:4.5, by 373.5g diesel oil, 305.7g water, 30.6g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of PGPR, 10.2g PEG400DL, 600rmp rotating speed, 280g hydrophobic associated polymer gelling agent for acid fluid is eventually adding, the high speed shear through 1000rmp forms uniform and stable quality point Number concentrates thickening agent for 28% Water-In-Oil association type acidifying.

0# diesel oil 36.25%, water 24.17%, hydrophobic associated polymer gelling agent for acid fluid 35%, polyglycerol polyricinoleate PGPR 3.27%, polyethylene glycol bilaurate PEG400DL1.31%；

Described hydrophobic associated polymer gelling agent for acid fluid be Methacrylamide/acryloyl-oxy dodecyl quaternary ammonium salt/ 2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is PGPR and PEG400DL (ratios 5:2), Preparation process is as follows：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 362.5g diesel oil, 241.7g water, 32.7g PGPR, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.1g PEG400DL, 600rmp rotating speed, finally adds Enter 350g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1500rmp forms uniform and stable mass fraction and is 35% Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 8

Preparation (the propylene glycol block polyether L62+ fatty alcohol polyoxy second of Water-In-Oil (W/O) association type acidifying concentration thickening agent Alkene ether AEO-3)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, propylene glycol block polyether L62 2.16%, AEO AEO-3 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is Methacrylamide/dodecyldimethylamine base allylic bromination Ammonium/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is L62 and AEO-3 (ratios 3:1), make Standby step is as follows：

At a temperature of 50 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g L62,7.2g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of AEO-3,600rmp rotating speed, is eventually adding 250g and dredges Water association polymer gelling agent for acid fluid, it is 25% oil bag that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water association type acidifying concentration thickening agent.

Atoleine 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, propylene glycol block polyether L62 2.43%, AEO AEO-3 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is Methacrylamide/nonyl pi-allyl dibrominated tetramethyl second Diamines/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is L62 and AEO-3 (ratios 7:3), Preparation process is as follows：

At a temperature of 55 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g atoleines, 308.4g water, 24.3g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of L62,10.4g AEO-3,600rmp rotating speed, finally 280g hydrophobic associated polymer gelling agent for acid fluid is added, the high speed shear through 1000rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

0# diesel oil 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, propylene glycol block polyether L62 2.64%, AEO AEO-3 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is Methacrylamide/dimethyl diallyl ammonium chloride/2- Acrylamide-2-methylpro panesulfonic acid salt copolymer, described compound emulsifying agent is L62 and AEO-3 (ratios 2:1) step, is prepared It is rapid as follows：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 396.2g diesel oil, 264.2g water, 26.4g L62, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.2g AEO-3,600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 9

Preparation (the Emulsifier EL-60 EL-10+ fatty alcohol polyoxies of Water-In-Oil (W/O) association type acidifying concentration thickening agent Vinethene AEO-4)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, Emulsifier EL-60 EL-10 2.16%, AEO AEO-4 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is Methacrylamide/(4- acrylamidos) Phenylhexyl two Methyl bromide ammonium/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is EL-10 and AEO-4 (ratio 3:1), preparation process is as follows：

At a temperature of 50 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g EL-10, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.2g AEO-4,600rmp rotating speed, is eventually adding 250g hydrophobic associated polymer gelling agent for acid fluid, it is 25% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Kerosene 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, Emulsifier EL-60 EL- 10 2.43%, AEO AEO-4 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is N tert butyl acrylamide/acryloyl-oxy myristyl quaternary ammonium Salt/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is EL-10 and AEO-4 (ratios 7:3), Preparation process is as follows：

At a temperature of 60 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g kerosene, 308.4g water, 24.3g EL- 10th, stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 10.4g AEO-4,600rmp rotating speed, finally adds Enter 280g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

White oil 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, Emulsifier EL-60 EL- 10 2.64%, AEO AEO-4 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is N tert butyl acrylamide/hexadecyldimethyl benzyl ammonium pi-allyl Ammonium bromide/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is EL-10 and AEO-4 (ratios 2:1), preparation process is as follows：

At a temperature of 70 DEG C, it is 6 to control profit mass ratio:4, by 396.2g white oils, 264.2g water, 26.4g EL-10, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.2g AEO-4,600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 10

Preparation (the methyl glycol fatty acid ester PGMS+ polyoxyethylene casters of Water-In-Oil (W/O) association type acidifying concentration thickening agent Oily HEL20)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, methyl glycol fatty acid ester PGMS 2.16%, Emulsifier EL-60 HEL20 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is N tert butyl acrylamide/octyl group pi-allyl dibrominated tetramethyl Base ethylenediamine/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is PGMS and HEL20 (ratios 3:1), preparation process is as follows：

At a temperature of 50 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g PGMS, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.2g HEL20,600rmp rotating speed, is eventually adding 250g hydrophobic associated polymer gelling agent for acid fluid, it is 25% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Atoleine 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, methyl glycol fatty acid ester PGMS 2.43%, Emulsifier EL-60 HEL20 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is N tert butyl acrylamide/dimethyl diallyl chlorination Ammonium/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is PGMS and HEL20 (ratios 7:3), Preparation process is as follows：

At a temperature of 65 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g atoleines, 308.4g water, 24.3g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of PGMS, 10.4g HEL20,600rmp rotating speed, finally 280g hydrophobic associated polymer gelling agent for acid fluid is added, the high speed shear through 1000rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

White oil 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, methyl glycol fatty acid ester PGMS 2.64%, Emulsifier EL-60 HEL20 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is that N tert butyl acrylamide/(4- acrylamidos) phenyl is pungent Base ditallowdimethyl ammonium bromide/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent for PGMS and HEL20 (ratios 2:1), preparation process is as follows：

At a temperature of 55 DEG C, it is 6 to control profit mass ratio:4, by 396.2g white oils, 264.2g water, 26.4g PGMS, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.2g HEL20,600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 11

Preparation (the paregal O O-3+ polyoxyethylene stearic acid esters SG- of Water-In-Oil (W/O) association type acidifying concentration thickening agent 6)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, paregal O O-3 2.16%, polyoxyethylene stearic acid ester SG-6 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is NIPA/acryloyl-oxy dodecyl quaternary ammonium Salt/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is O-3 and SG-6 (ratios 3:1), make Standby step is as follows：

At a temperature of 40 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g O-3,7.2g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of SG-6,600rmp rotating speed, is eventually adding 250g hydrophobic Association polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms the Water-In-Oil that uniform and stable mass fraction is 25% Association type acidifying concentration thickening agent.

Kerosene 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, paregal O O-32.43%, Polyoxyethylene stearic acid ester SG-6 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is NIPA/octadecyldimethyl pi-allyl Ammonium bromide/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is O-3 and SG-6 (ratios 7: 3), preparation process is as follows：

At a temperature of 60 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g kerosene, 308.4g water, 24.3g O-3, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 10.4g SG-6,600rmp rotating speed, is eventually adding 280g hydrophobic associated polymer gelling agent for acid fluid, it is 28% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Kerosene 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, paregal O O-32.64%, Polyoxyethylene stearic acid ester SG-6 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is NIPA/nonyl pi-allyl dibrominated tetramethyl Base ethylenediamine/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is O-3 and SG-6 (ratios 2: 1), preparation process is as follows：

At a temperature of 50 DEG C, it is 6 to control profit mass ratio:4, by 396.2g kerosene, 264.2g water, 26.4g O-3, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.2g SG-6,600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 12

The preparation (oleic acid ethylene glycol acid amides ODEA+ paregal O O-5) of Water-In-Oil (W/O) association type acidifying concentration thickening agent

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, oleic acid ethylene glycol acid amides ODEA2.16%, paregal O O-5 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is acrylamide/dimethyl diallyl ammonium chloride/2- propylene Amide groups -2- methyl propane sulfonic acid salt copolymers, described compound emulsifying agent is ODEA and O-5 (ratios 3:1), preparation process is such as Under：

At a temperature of 40 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, 21.6g ODEA, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 7.2g O-5,600rmp rotating speed, is eventually adding 250g Hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms the oil that uniform and stable mass fraction is 25% Bag water association type acidifying concentration thickening agent.

Kerosene 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, oleic acid ethylene glycol acid amides ODEA 2.43%, paregal O O-5 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is that NIPA/(4- acrylamidos) phenyl is pungent Base ditallowdimethyl ammonium bromide/2- acrylamide-2-methylpro panesulfonic acid salt copolymers, described compound emulsifying agent is ODEA and O-5 (ratio 7:3), preparation process is as follows：

At a temperature of 50 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g kerosene, 308.4g water, 24.3g Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of ODEA, 10.4g O-5,600rmp rotating speed, finally adds Enter 280g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp forms uniform and stable mass fraction and is 28% Water-In-Oil association type acidifying concentration thickening agent.

White oil 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, oleic acid ethylene glycol acid amides ODEA2.64%, paregal O O-5 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid be Methacrylamide/acryloyl-oxy myristyl quaternary ammonium salt/ Vinyl-sulfonate copolymer, described compound emulsifying agent is ODEA and O-5 (ratios 2:1), preparation process is as follows：

At a temperature of 65 DEG C, it is 6 to control profit mass ratio:4, by 396.2g white oils, 264.2g water, 26.4g ODEA, Stirring 30min forms stable water-in-oil emulsion under the well mixed emulsifications of 13.2g O-5,600rmp rotating speed, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, it is 30% that the high speed shear through 1000rmp, which forms uniform and stable mass fraction, Water-In-Oil association type acidifying concentration thickening agent.

Embodiment 13

Preparation (three Risorex PGIS 22s+fatty alcohol polyoxy of Water-In-Oil (W/O) association type acidifying concentration thickening agent Vinethene AEO-3)

0# diesel oil 36.06%, water 36.06%, hydrophobic associated polymer gelling agent for acid fluid 25%, the different tristearin of three polyglycereol two Acid esters 2.16%, AEO AEO-3 0.72%；

Described hydrophobic associated polymer gelling agent for acid fluid is N tert butyl acrylamide/acryloyl-oxy dodecyl quaternary ammonium Salt/styrene sulfonic acid salt copolymer, described compound emulsifying agent is three Risorex PGIS 22s and AEO-3 (ratios 3: 1), preparation process is as follows：

At a temperature of 50 DEG C, it is 5 to control profit mass ratio:5, by 360.6g diesel oil, 360.6g water, the polyglycereol of 21.6g tri- Stirring 30min forms stable water in oil emulsion under the well mixed emulsification of diisopstearate, 7.2g AEO-3,600rmp rotating speed Liquid, is eventually adding 250g hydrophobic associated polymer gelling agent for acid fluid, and the high speed shear through 1000rmp forms uniform and stable quality Fraction concentrates thickening agent for 25% Water-In-Oil association type acidifying.

Atoleine 37.69%, water 30.84%, hydrophobic associated polymer gelling agent for acid fluid 28%, three polyglycereol two are different hard Resin acid ester 2.43%, AEO AEO-3 1.04%；

Described hydrophobic associated polymer gelling agent for acid fluid is NIPA/acryloyl-oxy cetyl quaternary ammonium Salt/NVP copolymer, described compound emulsifying agent is that three Risorex PGIS 22s and AEO-3 (compare Example 7:3), preparation process is as follows：

At a temperature of 55 DEG C, it is 5.5 to control profit mass ratio:4.5, by 376.9g atoleines, 308.4g water, 24.3g Stirring 30min forms stabilization under the well mixed emulsification of three Risorex PGIS 22s, 10.4g AEO-3,600rmp rotating speed Water-in-oil emulsion, be eventually adding 280g hydrophobic associated polymer gelling agent for acid fluid, the high speed shear through 1000rmp is formed uniformly Stable mass fraction concentrates thickening agent for 28% Water-In-Oil association type acidifying.

White oil 39.62%, water 26.42%, hydrophobic associated polymer gelling agent for acid fluid 30%, the isostearic acid of three polyglycereol two Ester 2.64%, AEO AEO-3 1.32%；

Described hydrophobic associated polymer gelling agent for acid fluid is Methacrylamide/dimethyl diallyl ammonium chloride/benzene Vinyl-sulfonate copolymer, described compound emulsifying agent is three Risorex PGIS 22s and AEO-3 (ratios 2:1), make Standby step is as follows：

At a temperature of 60 DEG C, it is 6 to control profit mass ratio:4, by 396.2g white oils, 264.2g water, the polyglycereol of 26.4g tri- Stirring 30min forms stable Water-In-Oil under the well mixed emulsification of diisopstearate, 13.2g AEO-3,600rmp rotating speed Emulsion, is eventually adding 300g hydrophobic associated polymer gelling agent for acid fluid, and the high speed shear through 1000rmp forms uniform and stable matter It is 30% Water-In-Oil association type acidifying concentration thickening agent to measure fraction.

Embodiment application performance

The performance of Water-In-Oil association type acidifying concentration thickening agent prepared by embodiment 1~13

1st, stability

Embodiment 1~13 is prepared into Water-In-Oil association type acidifying concentration thickening agent and is respectively placed in 5 DEG C, 25 DEG C, 40 DEG C Under the conditions of after storage 120d concentration thickening agent system do not occur the phenomenons such as be layered, settle, concentration thickener system keeps stabilization, by This explanation, at 5~40 DEG C, the Water-In-Oil association type acidifying concentration thickening agent stabilization time prepared by the present invention is more than 120d, Have good stability.

2nd, application performance

The main performance index of gelling agent for acid fluid has sour molten time, viscosity, shear stability, heat endurance, slow property, matched somebody with somebody 5 property etc., are tested referring especially to People's Republic of China (PRC) oil and gas industry standard SY/T6214-1996《Gelling agent for acid fluid is commented Valency method》The Water-In-Oil association type acidifying concentration thickening agent prepared to embodiment 1~13 is evaluated.

If without explanation in experiment, each sample of gelling agent for acid fluid prepares 500mL, and wherein hydrophobic associated polymer acid solution is thickened The valid density of agent is 1.0wt%, and corrosion inhibiter is Mannich bases corrosion inhibiter, and concentration 1.0wt%, ferrous stability is hydroxyl Carboxylic acids ferrous stability, concentration is 1.0wt%, and concentration of hydrochloric acid is 20wt%.

(1), sour molten timing method

In hydrophobic associated polymer gelling agent for acid fluid mass concentration a certain amount of embodiment 1 is weighed for 1.0wt% ratio Hydrophobic associated polymer gelling agent for acid fluid used by~13 gained Water-In-Oil association types acidifying concentration thickening agent and correspondence embodiment is done Powder (in herein below and table 1 referred to as " copolymer dry powder ") is added in 20wt% hydrochloric acid solutions, and at 30 DEG C, 600rmp turns Speed is lower to be stirred, and acid solution is measured in 170s with six fast swing meters at interval of 30s (dry powder interval 5min)^-1When apparent viscosity, when Time when solution viscosity tends towards stability is sample dissolution time.

(2), apparent viscosity method of testing

The viscous acid that hydrophobic associated polymer gelling agent for acid fluid concentration is 1.0wt% is prepared, with six fast rotation viscometers 30 DEG C, 170s^-1The lower apparent viscosity for determining viscous acid at 30 DEG C.

(3), acid solution thermal stability determination method

The viscous acid that hydrophobic associated polymer gelling agent for acid fluid concentration is 1.0wt% is prepared, with six fast rotation viscometers 30 DEG C, 170s^-1The lower apparent viscosity for determining viscous acid at 30 DEG C, the there-necked flask with condenser pipe, thermostatted water are poured into by viscous acid After 60 DEG C of bath heating, constant temperature 4h, 30 DEG C are naturally cooled to, with six fast rotation viscometer 170s^-1Determine its apparent viscosity.After constant temperature It is thickening acid heat stability that the measured viscosity of cooling is multiplied by 100% with the ratio of the viscosity before constant temperature.

(4), acid solution shear stability assay method

The viscous acid that hydrophobic associated polymer gelling agent for acid fluid concentration is 1.0wt% is prepared, rotation viscometer rotating cylinder is placed in It is interior, in shear rate it is 170s with six fast rotation viscometers at 30 DEG C^-1Continuous shear stress 120min, during shearing, often The numerical value of an acid solution apparent viscosity is recorded every 20min.Shear the ratio of measured viscosity and the viscosity before shearing after 120min It is viscous acid shear stability to be multiplied by 100%.

(5), compatibility method of testing

It is 1.0wt% by hydrophobic associated polymer gelling agent for acid fluid concentration, corrosion inhibiter Mannich bases density of corrosion inhibitor is 1.0wt%, ferrous stability hydroxycarboxylic acid ferrous stability concentration is 1.0wt%, and concentration of hydrochloric acid is thick for 20wt%'s Change acid solution, which is placed in 60 DEG C of constant temperature oven, stands 48h, and observation whether there is precipitation.

Above-mentioned the performance test results are shown in Table 1, and table 1 is Water-In-Oil association type acidifying concentration thickening prepared by embodiment 1~13 The performance test results of agent

The performance test results of Water-In-Oil association type acidifying concentration thickening agent prepared by the embodiment 1~13 of table 1

Note：In table 1, " association type acidifying concentration thickening agent " abbreviation " concentration thickening agent ", " hydrophobic associated polymer acid solution is thick Agent dry powder " is referred to as " copolymer dry powder "

As it can be seen from table 1 the sour molten time ＜ of the Water-In-Oil association type acidifying concentration thickening agent prepared using the present invention 4min, substantially shortens with hydrophobic associated polymer gelling agent for acid fluid dry powder used to its sour molten time, therefore illustrates in thickening agent In terms of dissolving, the present invention has obvious advantage, is conducive to site operation.Water-In-Oil association type acidifying concentration thickening agent is apparent viscous The performances such as degree, heat endurance, shear stability are also better than correspondence hydrophobic associated polymer gelling agent for acid fluid dry powder, and Water-In-Oil is formed Mould assembly acidifying concentration thickening agent and correspondence hydrophobic associated polymer gelling agent for acid fluid dry powder and acid additive compatibility are good, Do not precipitate.

Water-In-Oil association type acidifying concentration thickening agent excellent performance prepared by the present invention can be illustrated by result above, had Good application prospect.

The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims

1. a kind of Water-In-Oil association type acidifying concentration thickening agent, it is characterised in that include the component of following mass percent：

18wt%~45wt% dispersed phase, the dispersed phase is water；

20wt%~40wt% hydrophobic associated polymer gelling agent for acid fluid；

2.5wt%~6wt% compound emulsifying agent, the compound emulsifying agent is the emulsifying agent that HLB value is 3~7 and HLB value is 8 The compound emulsifying agent of~10 emulsifying agent compounding；

Above-mentioned each component content sum is 100wt%.

2. Water-In-Oil association type according to claim 1 acidifying concentration thickening agent, it is characterised in that the HLB value is 3~ The mass ratio for the emulsifying agent that 7 emulsifying agent is 8~10 with HLB value is (4~6):(1~3).

3. Water-In-Oil association type according to claim 1 acidifying concentration thickening agent, it is characterised in that the HLB value is 3~ 7 emulsifying agent is selected from propylene glycol monostearate BPMS, PGML BPML, diethylene glycol monostearate The double stearate DEGDS of DEGMS, diethylene glycol, polyglycerol polyricinoleate PGPR, polyethylene glycol dioleic acid ester PEG400DO, oil Sour polyoxyethylene ester A-103, methyl glycol fatty acid ester PGMS, oleic acid diethyl amide ODEA, paregal O O-3, polyoxyethylene One in castor oil EL-10, Emulsifier EL-60 EL-12, propylene glycol block polyether L62 and three Risorex PGIS 22s Plant or a variety of；

The HLB value for 8~10 emulsifying agent be selected from AEO AEO-3, AEO AEO-4, Emulsifier EL-60 EL-20, Emulsifier EL-60 HEL20, diacetyl tartarate list double glyceride DATEM, stearic acid gather Oxygen vinyl acetate SG-6, laurate APEO LAE-4, paregal O O-5, polyoxyethylene oleic acid ester A-105 and polyethylene glycol One or more in bilaurate PEG400DL.

4. Water-In-Oil association type acidifying concentration thickening agent according to claim 1, it is characterised in that the compound emulsifying agent Selected from propylene glycol monostearate BPMS and paregal O O-5 formation compound emulsifying agent, PGML BPML with Compound emulsifying agent, polyethylene glycol dioleic acid ester PEG400DO and the aliphatic alcohol polyethenoxy of Emulsifier EL-60 EL-20 formation What compound emulsifying agent, diethylene glycol monostearate DEGMS and the laurate APEO LAE-4 of ether AEO-3 formation were formed Compound emulsifying agent, polyoxyethylene oleic acid ester A-103 and diacetyl tartarate list double glyceride DATEM formation compound emulsifying agent, The compound emulsifying agent of the double stearate DEGDS and polyoxyethylene oleic acid ester A-105 formation of diethylene glycol, polyglycerol polyricinoleate Compound emulsifying agent, propylene glycol block polyether L62 and the poly alkyl alcohol of PGPR and polyethylene glycol bilaurate PEG400DL formation Compound emulsifying agent, Emulsifier EL-60 EL-10 and the AEO AEO-4 of oxygen vinethene AEO-3 formation are formed Compound emulsifying agent, methyl glycol fatty acid ester PGMS and Emulsifier EL-60 HEL20 formation compound emulsifying agent, paregal O Compound emulsifying agent, oleic acid diethyl amide ODEA and the paregal O O-5 that O-3 is formed with polyoxyethylene stearic acid ester SG-6 are formed Compound emulsifying agent or three Risorex PGIS 22s and AEO AEO-3 formation compound emulsifying agent.

5. Water-In-Oil association type acidifying concentration thickening agent according to claim 1, it is characterised in that the hydrophobic association gathers Compound gelling agent for acid fluid has molecular formula shown in formula (I)：

Wherein, A is the monomeric unit of hydrophilic monomer, and the hydrophilic monomer is acrylamide, Methacrylamide, the N- tert-butyl groups third Any one or more in acrylamide and NIPA；

B is the monomeric unit of cation hydrophobic monomer, and the cation hydrophobic monomer is acryloyloxyalkyl quaternary ammonium salt, long alkane Based quaternary ammonium salt unsaturated monomer, polyoxyethylene base dibrominated tetramethylethylenediamine, diallyl quaternary ammonium and (4- acrylamides Base) any one or more in phenylalkyl ditallowdimethyl ammonium bromide；

C is the monomeric unit of function monomer, and the function monomer is 2- acrylamide-2-methylpro panesulfonic acids or its salt, ethene Any one or more in base sulfonic acid or its salt, styrene sulfonic acid or its salt and NVP；

X, y, z is the mole percent of monomeric unit in hydrophobic associated polymer；Y is that 0.1%~20%, z is 0~30%；x、 Y, z summation are 1.

6. Water-In-Oil association type according to claim 1 acidifying concentration thickening agent, it is characterised in that described with the mutual not phase of water One or more of the organic solvent of appearance in diesel oil, kerosene, atoleine and white oil.

7. a kind of preparation method of Water-In-Oil association type acidifying concentration thickening agent as described in claim 1~6 any one, its It is characterised by, comprises the following steps：

B hydrophobic associated polymer gelling agent for acid fluid) is added into the water-in-oil emulsion, is mixed, Water-In-Oil association is obtained Type acidifying concentration thickening agent.

8. preparation method according to claim 6, it is characterised in that step A) in, the temperature of the mixing is 35 ~70 DEG C, the rotating speed of the mixing is 300~800rmp, and the time of the mixing is 20~60min.

9. preparation method according to claim 6, it is characterised in that step B) in, the mixing temperature is 35~ 70 DEG C, the rotating speed of the mixing is 600~2000rmp, and the mixing time is 40~120min.

10. a kind of gelling agent for acid fluid, it is characterised in that including the Water-In-Oil association type acid described in Claims 1 to 5 any one Change Water-In-Oil association type acidifying concentration thickening agent prepared by concentration thickening agent or claim 6~9 any one preparation method.