Can suspended prop and preparation method thereof in well fracturing water
Technical field
The present invention relates to well fracturing volume increase field, can suspended prop and its preparation side more particularly in water blanket
Method.
Background technology
Pressure break is one of major measure of well production increment, is that fracturing fluid is injected into stratum with high-pressure pump, makes splitting for stratum
Seam expands and causes new crack and insert proppant, so as to improve the permeability on stratum.Proppant and fracturing fluid must for pressure break
The material for needing.
Based on haydite and quartz sand, ceramsite propping agent has higher resistant to breakage energy to conventional proppants in the market
Power (52MPa percentages of damage are generally less than 5%), sphericity is good, and flow conductivity is strong, but relatively denser, it is desirable to fracturing fluid viscosity compared with
Height, difficulty of construction is larger, more serious to delivery pump and pipe wear, makes operating expenses and the invisible increase of equipment safety risk;
Natural siliceous sand relative density is relatively low, is easy to fracturing fluid to carry conveying, but due to its low intensity, suitable reservoir stress is less than
The stratum of 35MPa.In one layer of resin film of conventional proppants surface coating, referred to as resin coated propping agent, resin coating is supported
Agent can be greatly lowered percentage of damage, turbidity, the acid solubility of proppant, improve the flow conductivity of proppant and extend pressure break timeliness
Property.The effect of fracturing fluid is transmission pressure, realizes that live stratum manufacture crack and carrying proppant enter crack.
Chinese patent application 201510266248.7 disclose it is a kind of for riverfrac treatment from suspended prop, including kernel
Particles of aggregates and the composite resin clad for being coated on kernel particles of aggregates surface;The composite resin clad is by following weight
The component composition of number:1.5~4.5 parts of water-soluble resin, 0.8~2 part of water-swellable polymer, 0.1~0.2 part of cross-linking agent,
0.05~0.1 part of dispersant;Wherein water-soluble resin and the mass ratio of the kernel particles of aggregates are 1.5~4.5:100.It is described
Water-soluble resin be water-soluble epoxy resin, water soluble polyurethane resin, water soluble phenol resin, water soluble acrylic resin with
And any one in their water-soluble modified polymer.The water-swellable polymer is polyacrylamide, hydroxypropyl fibre
Dimension element or hydroxyethyl cellulose.The cross-linking agent is nitroglycerin, glycerol triacetate, poly(ethylene oxide) or poly(propylene oxide).
The problem that the patent is present is the water-soluble resin (water-soluble epoxy resin, water soluble polyurethane resin, water soluble phenolic resin
Fat, water soluble acrylic resin) it is that physics is coated on quartz sand or haydite surface, there is no curing reaction, by this kind certainly
Suspended prop is put into when stirring in clear water, and water-soluble resin dissolves in water, be coated on quartz sand or haydite surface can
Swollen polymer will be separated with quartz sand or haydite, and quartz sand or haydite can be settled, and polymers capable of swelling does not have suspension effect.
Chinese patent application 201410479945.6 disclose one kind from suspended prop, it is described from suspended prop be
Adhesion at least one of which water-soluble high-molecular material is formed on aggregate, is expanded and molten in water after mixing with natural water at normal temperatures
Solution, maintains in suspended state and within a certain period of time the state.The consumption of the water-soluble high-molecular material is aggregate consumption
0.1~1.5Wt%, the water-soluble high-molecular material be selected from polycaprolactone, guanidine glue, polyvinyl acetate, polyvinyl alcohol
With one or more in polyacrylamide, the guanidine glue is hydroxypropyl guar and/or carboxy-methyl hydroxy propyl guanidine glue, described poly- third
Acrylamide is PAMA.The water-soluble high-molecular material sticked in by binding agent and formed on aggregate, described
The consumption of binding agent is aggregate 0.1~0.7Wt% of consumption, and the binding agent is selected from phenolic resin, epoxy resin, unsaturated polyester (UP)
Any one or more in resin, the phenolic resin is thermoplastic phenolic resin and/or thermosetting phenolic resin;The ring
Oxygen tree fat uses the epoxy resin that epoxide equivalent is 0.09-0.14mol/100g;The unsaturated polyester resin for adjacent benzene-type not
Saturated polyester resin, metaphenylene unsaturated polyester resin, xylol type unsaturated polyester resin, bisphenol A-type unsaturated polyester (UP) tree
One or more in fat, halo unsaturated polyester resin, vinyl ester resin;The resin is respectively a) epoxy resin, or
B) unsaturated polyester resin, or c) thermoplasticity and/or thermosetting phenolic resin, corresponding, the firming agent is respectively a) fat
Fat race amine and its addition product, tertiary amine and its salt, aromatic amine and its modified body, imidazoles, macromolecule performed polymer, b) acyl peroxide
Class, lipid peroxidation, c) paraformaldehyde or hexamethylenetetramine.The problem that the patent is present is in described water soluble polymer material
In material, water insoluble (polycaprolactone has excellent biocompatibility, Memorability, life for polycaprolactone and polyvinyl acetate
Biodegradable etc., but it is water insoluble;Polyvinyl acetate is colourless viscous fluid or pale yellow transparent glass particles, softening point
About 38 DEG C, it is impossible to dissolve each other with fat and water);Guanidine glue, polyvinyl alcohol and polyacrylamide are soluble in water, only when guanidine glue, gather
Vinyl alcohol and polyacrylamide when being cross-linked to form gel could imbibition, but this patent is not to guanidine glue, polyvinyl alcohol and poly-
Acrylamide is crosslinked, and does not have the effect that water suction expands proppant volume, is only to increase the viscosity of water.Also water solublity
The binding agent that macromolecular material is sticked on aggregate by binding agent is selected from phenolic resin, epoxy resin, unsaturated polyester resin
In any one or more, such binding agent is pressed and water not expansion is met after the solidification of this patent condition, on the one hand limits binding agent
Internal water-soluble high-molecular material expansion, the water-soluble high-molecular material of another aspect adhesive surface takes off because dissolving is easy
From proppant body.
Chinese patent application 201280042615.X discloses modified proppant, and the modified proppant contains proppant
Grain and hydrogel coating.Wherein, the hydrogel coating is applied the surface for being overlying on proppant particles, and local on a surface
Change to produce modified proppant.Hydrogel coating can the polymer containing water-swellable.In embodiments, hydrogel coating with
Liquid apply be overlying on can be containing solvent or carrier fluid surface;By removing solvent or carrier fluid, liquid hydrogel coating can
It is changed into dry hydrogel coating.In embodiments, contact with aqueous fluid, dry hydrogel coating expansion volume,
To form the swelling hydrogel coating with the thickness more than dry hydrogel coating at least about 10%.In embodiment
In, hydrogel coating contains the polymer selected from group consisting of:Polyacrylamide, polyacrylic acid, acrylamide and third
The copolymer of olefin(e) acid salt, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, carboxymethyl guar, carboxylic
Methylhydroxypropyl guar gum, the emulsion polymer of hydrophobic association swellable and latex polymer.In embodiments, it is modified and supports
Agent also contains cross-linking agent;The cross-linking agent can contain covalent crosslinking agent, and the covalent crosslinking agent can be containing being selected from
The functional group of group consisting of:Epoxide, anhydride, aldehyde, diisocyanate and carbodiimide.In embodiments, covalently
Cross-linking agent may be selected from the group for consisting of:Polyethylene Glycol, diglycidyl ether, epichlorohydrin, maleic anhydride, formaldehyde, second two
Aldehyde, glutaraldehyde, toluene di-isocyanate(TDI) and methylenediphenyl diisocyanates, 1- ethyl -3- (3- dimethylaminopropyls)
Carbodiimide.In embodiments, the modified proppant is also containing the alcohol selected from group consisting of:Ethylene glycol, the third two
Alcohol, glycerol, propanol and ethanol.The problem that the patent is present is that hydrogel coating applies that be overlying on can be containing solvent or carrier current with liquid
The surface of body, by removing solvent or carrier fluid, liquid hydrogel coating can be changed into dry hydrogel coating.The process one
Aspect coating dry run is complicated;On the other hand, by hydrogel with proppant body bonding, hydrogel is in pressure break for no binding agent
Easily the effect of increase proppant volume is not had when stirring in process water from proppant surface disengaging.
In well fracturing stimulation process, in order to reduce the consumption of fracturing fluid and reduce injury of the fracturing fluid to stratum,
Requirement to proppant is that intensity is higher and density is lower, realizes that riverfrac treatment is most preferable.But it is adapted to propping up for pressing crack construction at present
Support agent apparent density is more than 2.50g/cm3, it is impossible to meet the condition suspended in water, it is impossible to realize riverfrac treatment.
The content of the invention
Problems to be solved by the invention
Present invention aim to address in above-mentioned prior art, there are the following problems:Or from suspended prop proppant table
Hydrogel layer on face easily departs from pressure break whipping process with proppant body, does not have increase proppant volume and reaches suspension
Purpose, or selected binding agent is dissolved in after water or the solidification of selected binding agent in water without dilatancy, affect the water can be swollen
The performance of swollen polymer, or selected water-soluble high-molecular material such as guanidine glue, polyvinyl alcohol and polyacrylamide etc. are without solidifying
Gel, dissolves not expansion in water.
For solution to problem
In a kind of present invention water of exploitation can suspended prop and preparation method thereof, the proppant can not only suspend in water,
And the hydrogel layer of proppant surface in pressure break whipping process without departing from proppant, realize the body of real increase proppant
Accumulate, reach the purpose that can be suspended in fracturing process.
The present invention water in can suspended prop include proppant aggregate, the boundary between expanding layer and aggregate and expanding layer
Face transition zone;The expanding layer comprising hydrogel dry powder and for bond hydrogel dry powder and in water swellable binding agent;
The interface transition layer includes the epoxy resin and/or thermoplastic phenolic resin as interface transition layer resin.
The expanding layer can be comprising polyurethane binder and hydrogel dry powder.In this case, polyurethane binder
The 0.1~2% of aggregate weight can be accounted for, hydrogel dry powder can account for the 0.1~4% of aggregate weight;Interface transition layer can be accounted for
The 0.1~4% of aggregate weight.The proppant of the proportion of composing not only has from outstanding function, and due to interfaces transition in water
Layer solves aggregate and is firmly bonded sex chromosome mosaicism between expanding layer, and proppant suspension is stablized in pressure break course of conveying, together
When interface transition layer can strengthen the intensity of aggregate, substantially reduce the percentage of damage of aggregate.
When the interface transition layer includes epoxy resin, firming agent used can be more selected from alicyclic polyamine, aromatic series
Amine, modified alicyclic polyamine and/or modified aromatic race polyamines, the consumption of firming agent accounts for the 10~40% of weight epoxy;When
When the interface transition layer includes thermoplastic phenolic resin, firming agent used can be hexamethylenetetramine, and firming agent accounts for phenolic aldehyde
The 10~20% of weight resin.
Additionally, the interface transition layer can include coupling agent, the coupling agent can account for the 0.5 of transition zone weight resin
~2%.The coupling agent can be silane coupler, selected from gamma-aminopropyl-triethoxy-silane, N, N- double (beta-hydroxyethyls)-
γ-aminocarbonyl propyl front three oxosilane, anilino- methylene triethoxysilane, γ-glycidyl ether propyl trimethoxy silicane.
The coupling agent is 0.1~3 with the ratio of transition zone weight resin:100, preferably 0.5~2:100.The selection of the coupling agent and
Proportioning can well reinforced resin with the adhesion strength between aggregate.
Described polyurethane binder can be made up of polyisocyanates and water-soluble sulfonate PEPA.
In order to realize the purpose of the present invention, the present invention provides the synthetic method of sulfonate polyester polyol.The method includes
Following steps:Sulfonate, binary acid and dihydroxylic alcohols are made in the presence of esterification and alcoholysis catalysts, is reacted in 140~175 DEG C, when
The limpid transparent, acid number of reactant less than after 90mgKOH/g, add binary acid and/or dibasic acid anhydride and trihydroxylic alcohol in 140~
200 DEG C of generation polycondensation reactions, 1mgKOH/g, hydroxyl value are less than between 50~100mgKOH/g to acid number, obtain target product, its
The usage amount of middle sulfonate is 1 with the mol ratio of binary acid and/or total usage amount of dibasic acid anhydride:20~4, preferably 1:10~
5, trihydroxylic alcohol is 1 with the mol ratio of dihydroxylic alcohols:30~10, preferably 1:20~15, the binary acid for adding first adds with second
The binary acid for entering and/or the mol ratio of dibasic acid anhydride are 1:0.8~5, preferably 1:1~3, more preferably 1:2, dihydroxylic alcohols and trihydroxylic alcohol
It is 1.05~1.3 with the mol ratio of binary acid and/or total usage amount of dibasic acid anhydride:1.The sulfonate is preferably isophthalic diformazan
Disulfonate acid or Phloroglucinol Derivatives or its mixture.
In the water of the present invention can the preparation method of suspended prop comprise the steps:
1) aggregate is heated, the interface transition layer constituent containing coupling agent is added under agitation, make transition zone overlay film
On aggregate, add firming agent and solidified, the coupling agent accounts for the 0.5~2% of transition layer weight;
2) it is added to the water the binding agent and hydrogel dry powder of swellable and stirs;
3) material cooled down, crush and sieve.
Invention effect
In the water that the present invention is provided can suspended prop not only proppant particles can suspend in water, and proppant table
The hydrogel layer in face in pressure break whipping process without departing from proppant particles body, the real volume for realizing increase proppant,
The purpose that can be suspended in fracturing process is reached, while guar gum or modified guar used by the current routine pressure break of hydrogel amount ratio
Consumption declines to a great extent, little to formation damage, and the broken glue of hydrogel completely, is conducive to improving flow conductivity, and pressing crack construction technique
Simply, low cost.
Specific embodiment
What the present invention was provided includes proppant aggregate, expanding layer and for solving aggregate and expanding layer from suspended prop
Between interface problem interface transition layer.
The proppant aggregate can be proppant aggregate commonly used in the art, as long as it meets SY/T5108-2014
《Hydraulic fracturing and gravel packing operations recommend method with proppant performance test》Specified in index.Proppant in the present invention
Aggregate preferably uses natural siliceous sand and/or haydite.
In order to improve the intensity of proppant and make aggregate bonding with expanding layer firmly, with epoxy resin and/or thermoplasticity
Phenolic resin is as interface transition layer resin to aggregate overlay film, it is ensured that the intensity and interface performance of proppant.In this case,
The resin can account for the 0.5~4% of aggregate weight, and preferably 1.0~3%.If in order to individually improve proppant aggregate with it is swollen
The interface problem of swollen layer, the resin can account for the 0.2~1% of aggregate weight, in the case of the resin demand proppant into
This is than relatively low.
When the interface transition layer resin is epoxy resin, the preferred inexpensive and good bisphenol type epoxy of coating technique
Resin, for example, can be selected from one or more in E-21, E-20, E-14, the E-13 being obtained commercially.For the epoxy resin
Firming agent can be alicyclic polyamine, modified alicyclic polyamine, aromatic polyamine and/or modified aromatic race polyamines.Wherein, institute
State alicyclic polyamine and be preferably selected from isophorone diamine, double aminocyclohexanes, diamino-dicyclohexyl methane, adjacent diamidogen methyl ring
One or more in pentane and Meng's alkane diamidogen.The aromatic polyamine is preferably selected from m-xylene diamine, diamino-diphenyl first
One or more in alkane, m-diaminobenzene..The modified alicyclic polyamine and modified aromatic race polyamines are preferably commercial can purchase
The corresponding modified polyamine for arriving, consumption is preferably the 5~30% of weight epoxy.The interface transition layer resin is phenolic resin
When (preferably, the softening point of phenolic resin used is more than 90 DEG C, and 150 DEG C of rates of polymerization are less than 90 seconds, and free phenol content is less than
0.5 weight %, the interface transition layer resin for meeting the condition meets environmental requirement, and disclosure satisfy that good overlay film performance), institute
Can be hexamethylenetetramine with firming agent, its consumption is preferably the 10~20% of phenolic resin weight.The firming agent of the ratio
Thermoplastic phenolic resin film strength can be made to be strengthened well.
The coupling agent can be selected from various coupling agents well known by persons skilled in the art.In order to improve interface transition layer tree
The adhesive strength of fat and proppant aggregate, the preferably coupling agent are silane coupler.The example of silane coupler includes γ-ammonia
Propyl-triethoxysilicane, anilino- methylene triethoxysilane, γ-glycidyl ether propyl trimethoxy silicane etc..It is described
The consumption of coupling agent is preferably the 0.1~2% of interface transition layer weight resin, and more preferably 0.5~1%.The coupling agent
Selection and proportioning can well reinforced resin with the adhesive strength between aggregate.
According to a preferred embodiment of the invention a, when interface transition layer resin of the invention is epoxy resin, the tree
The epoxide number of fat is more than 0.12 mole/100 grams;When the interface transition layer resin of the present invention is thermoplastic phenolic resin, the resin
Softening point be more than 85 DEG C, 150 DEG C of rates of polymerization are less than 120 seconds, and free phenol content is less than 0.5%.Meet the boundary of above-mentioned condition
Face transition zone resin meets environmental requirement, and disclosure satisfy that good overlay film performance.
According to a preferred embodiment of the invention a, in water of the invention can the expanding layer of suspended prop include poly- ammonia
Ester adhesive and hydrogel dry powder, polyurethane binder is made up of polyisocyanates and water-soluble sulfonate PEPA.
Sulfonate for preparing the sulfonate polyester polyol is preferably sodiosulfoisophthalic acid or isophthalic diformazan
Dimethyl phthalate sodium sulfonate or its mixture.In the preparation method of sulfonate polyester polyol, sodiosulfoisophthalic acid or
Phthalic dimethyl ester sulfonate sodium is 1 with the mol ratio of binary acid and/or dibasic acid anhydride:20~4, preferably 1:10~5;Ternary
Alcohol is 1 with the mol ratio of dihydroxylic alcohols:30~10, preferably 1:20~15.The trihydroxylic alcohol can be glycerol or trihydroxy methyl third
Alkane or its mixture.The binary acid can for M-phthalic acid, p-phthalic acid, adipic acid, decanedioic acid, fumaric acid,
Itaconic acid, citraconic acid or chloro maleic acid or its mixture, the dibasic acid anhydride can be HHPA, phthalic anhydride, Na Di
Gram anhydride, THPA and maleic anhydride or its mixture;The dihydroxylic alcohols can for ethylene glycol, diglycol,
Triethylene-glycol, tetraethylene-glycol, PEG-4000, Polyethylene Glycol -600, PEG-8 00, Polyethylene Glycol -
1000th, neopentyl glycol or its mixture.
Sulfonate polyester polyol synthesis technique of the present invention is two-step method, can specifically be comprised the steps:
First by sodiosulfoisophthalic acid or Phloroglucinol Derivatives, binary acid (half of total acid content), dihydroxylic alcohols and ester
Change and alcoholysis catalysts are added in reactor, lead to nitrogen protection, be warmed up to 120 DEG C and start stirring, after being heated to 140 DEG C, progressively
170 DEG C are warmed up to, in 170~175 DEG C of insulations, until acid number is less than 90mgKOH/g and reactant is limpid transparent, are cooled to
Less than 160 DEG C, remaining binary acid (or anhydride) and trihydroxylic alcohol are added, after being incubated one hour at 140~160 DEG C, be progressively warmed up to
190 DEG C, control interior temperature in temperature-rise period and be less than 103 DEG C, in 190~200 DEG C of insulations, when acid number is less than 90mgKOH/g,
It is evacuated to acid number and drops to below 1mgKOH/g, obtains target product.
Wherein described esterification and alcoholysis catalysts can be the compound of zinc, titanium or stannum, such as zinc acetate, dibutyl oxidation
Stannum and butyl titanate, its consumption accounts for the 0.005~0.2% of all materials weight, and suitable consumption is 0.05~0.1%.
The polyisocyanates of composition polyurethane binder can be selected from phenylene diisocyanate, toluene di-isocyanate(TDI), diformazan
Phenylmethane diisocyanate, ethylbenzene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, polymethylene
Many phenyl isocyanate (abbreviation PAPI), its average functionality is 2.5~2.6.
The hydrogel dry powder that the present invention is used is the polymer that a class has three-dimensional net structure, can absorb big in water
Amount moisture and it is swelling, and can continue to after swelling keep its original structure and be not dissolved.Every water solublity or hydrophilic
Macromolecule, by certain chemical crosslinking or physical crosslinking, hydrogel can be formed.These macromolecules can be divided by its source
For natural and two big class of synthesis.Natural hydrophilic macromolecule includes polysaccharide (starch, cellulose, alginic acid, shitosan etc.)
With polypeptide (collagen, polylysine, poly- L- glutamic acids etc.).The hydrophilic high mol of synthesis includes acrylic acid and its derivatives class
(polyacrylic acid, polymethylacrylic acid, polyacrylamide, poly- N- are poly- for acrylamide etc.).
According to a preferred embodiment of the invention a, in the preparation method of proppant of the present invention, in step 1) middle general
Aggregate is heated between 180~220 DEG C, is then lowered the temperature, and when temperature is reduced to 180 ± 20 DEG C, adds the transition containing coupling agent
Layer resin, the time of stirring is 40 ± 20 seconds, adds the time that firming agent is solidified to be 90 ± 30 seconds, not only ensures transition zone
Resin solidification is completely and resin film also will not wear and tear;Step 2) in add hydrogel dry powder before and after be separately added into water
The constituent sulfonate polyester polyol of the binding agent of middle swellable and polyisocyanates, the stirring of sulfonate polyester polyol
Time is 40 ± 10 seconds, and the mixing time of hydrogel dry powder is 40 ± 10 seconds, and the time of the stirring solidification of polyisocyanates is 120
± 20 seconds.Hydrogel dry powder can be so set to be uniformly coated on the outer surface of interface transition layer, it is ensured that sulfonate polyester is more
First alcohol and polyisocyanates completion of cure and hydrogel dry powder also will not wear and tear, while production efficiency is improved.In addition, first
Lower the temperature after intensification, high temperature can remove moisture and a small amount of impurity in aggregate, satisfactory temperature is then dropped to again, can be with
Strengthen film intensity.
Below the present invention is explained in further detail by the way of embodiment.
It is, in order to preferably further understand the present invention, to the invention is not limited in the optimal reality to provide following embodiments
Apply mode.Embodiment is not construed as limiting to present disclosure and protection domain, any under the enlightenment of the present invention or by originally
The product with feature described in claim or method that invention is combined and draws with the feature of other prior arts, fall
Within protection scope of the present invention.
The raw materials used source of embodiment:
Thermoplastic phenolic resin is available commercially from Shandong Shengquan Chemical Industry Co., Ltd. or Nantong Sumitomo Bakelite company limited, double
Phenol A type epoxy resin is available commercially from Ba Ling petrochemical industries Co., Ltd, and hydrogel dry powder is available commercially from Beijing Hua Ruixiang science and technology to be had
The A1 hydrogels dry powder of limit company or the K4 hydrogel dry powder of Renqiu Quan Xing Chemical Co., Ltd.s.
Unreceipted particular technique or condition person in each embodiment, according to the routine techniquess described by document in the art or
Condition is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can pass through commercially available customary commercial.
Embodiment 1
Sulfonate polyester polyol synthetic example 1:By 11.1 kilograms of Phloroglucinol Derivatives, isophthalic diformazan
In 18.7 kilograms of acid, 15.9 kilograms of diglycol, 50 grams of addition reactors of 27.0 kilograms of triethylene-glycol and zinc acetate,
Logical nitrogen protection, is warmed up to 120 DEG C and starts stirring, is heated to 140~160 DEG C and is incubated one hour, is progressively warmed up to 170 DEG C,
170~175 DEG C of insulations, when acid number is less than 90mgKOH/g and reactant is completely limpid transparent, cool to 140 DEG C, add benzene
0.67 kilogram of 22.2 kilograms of acid anhydride and trimethylolpropane, are warmed up to 140~160 DEG C and are incubated one hour, are progressively warmed up to 190 DEG C,
Interior temperature is controlled in temperature-rise period and is less than 103 DEG C, in 190~200 DEG C of insulations, when acid number is less than 60mgKOH/g, evacuation
Below 1mgKOH/g is dropped to acid number, sulfonate polyester polyol, hydroxyl value 46.2mgKOH/g is obtained.
Embodiment 2
Sulfonate polyester polyol synthetic example 2:By 13.4 kilograms of sodiosulfoisophthalic acid, 14.8 kilograms of phthalic anhydride,
In 16.9 kilograms of diglycol, 28 grams of addition reactors of 32.0 kilograms of tetraethylene-glycol and Dibutyltin oxide, lead to nitrogen
Gas shielded, is warmed up to 120 DEG C and starts stirring, is heated to 140~160 DEG C and is incubated one hour, is progressively warmed up to 170 DEG C, 170~
175 DEG C of insulations, 160 DEG C are cooled to when acid number is less than 90mgKOH/g, add 22.2 kilograms of phthalic anhydride and trimethylolpropane 2.6
Kilogram, it is warmed up to 140~160 DEG C and is incubated one hour, 190 DEG C are progressively warmed up to, interior temperature is controlled in temperature-rise period and is less than 103
DEG C, in 190~200 DEG C of insulations, when acid number is less than 60mgKOH/g, it is evacuated to acid number and drops to below 1mgKOH/g, obtain sulphur
Hydrochlorate PEPA, hydroxyl value 57.6mgKOH/g.
Embodiment 3
Sulfonate polyester polyol synthetic example 3:By 22.2 kilograms of Phloroglucinol Derivatives, phthalic anhydride 11.1
Kilogram, in 33.75 kilograms of triethylene-glycol, 45.0 kilograms of Polyethylene Glycol and 56 grams of addition reactors of zinc acetate, lead to nitrogen and protect
Shield, is warmed up to 120 DEG C and starts stirring, is heated to 140~160 DEG C and is incubated one hour, 170 DEG C is progressively warmed up to, 170~175
DEG C insulation, when acid number is less than 90mgKOH/g 160 DEG C are cooled to, and add 22.2 kilograms of phthalic anhydride and trimethylolpropane 5.4 thousand
Gram, it is warmed up to 140~160 DEG C and is incubated one hour, 190 DEG C are progressively warmed up to, interior temperature is controlled in temperature-rise period and is less than 103
DEG C, in 190~200 DEG C of insulations, when acid number is less than 60mgKOH/g, it is evacuated to acid number and drops to 1mgKOH/g, obtain sulfonate
PEPA, hydroxyl value 52.1mgKOH/g.
Embodiment 4
During self-control puddle mixer is put into after 3 kilograms of particle diameters are heated to into 220 DEG C for the quartz sand of 850/425 μm (20/40 mesh)
Stirring, adds 45 grams of epoxy resin and γ -0.3 gram of glycidyl ether propyl trimethoxy silicane and stirs after being cooled to 200 DEG C
40 seconds, add 5.4 grams of diaminodiphenyl-methane and stir solidification 150 seconds;Cool to and add after 140 DEG C prepared by embodiment 1
18.6 grams of sulfonate polyester polyol is simultaneously stirred 40 seconds, adds 60 grams of hydrogel dry powder to stir 40 seconds, adds toluene diisocynate
The stirring solidification of 5.4 grams of ester, until granule is completely dispersed, cools down, sieves, and obtain the present invention can suspended prop.
Embodiment 5 (comparative example)
During self-control puddle mixer is put into after 3 kilograms of particle diameters are heated to into 220 DEG C for the quartz sand of 850/425 μm (20/40 mesh)
Stirring, adds 18.6 grams of the sulfonate polyester polyol of the preparation of embodiment 1 and stirs 40 seconds after being cooled to 140 DEG C, add water-setting
60 grams of glue dry powder is stirred 40 seconds, adds 5.4 grams of stirring solidifications of toluene di-isocyanate(TDI), until granule is completely dispersed, cooling, mistake
Sieve, obtains contrasting proppant.
Embodiment 6 (comparative example)
During self-control puddle mixer is put into after 3 kilograms of particle diameters are heated to into 220 DEG C for the quartz sand of 850/425 μm (20/40 mesh)
Stirring, adds 18.6 grams of phenolic resin and stirs 40 seconds after being cooled to 180 DEG C, add 60 grams of hydrogel dry powder to stir 40 seconds, plus
Enter the stirring solidification of hexamethylenetetramine solution 3.7, until granule is completely dispersed, cools down, sieve, obtain contrasting proppant.
The embodiment 4,5 of table 1. and 6 Comparative results
Note:150ml beakers add 20 grams of proppants, plus 100ml water, observation proppant expansion multiple and shelling phenomenon
Embodiment 7
By low close haydite (the prosperous high-tech of the Pingxiang City hundred million ceramics company limited that 3 kilograms of particle diameters are 850/425 μm (20/40 mesh)
Production, bulk density 1.35g/cm3, apparent density 2.38g/cm3) be heated to 220 DEG C after be put into self-control puddle mixer in stir, cooling
60 grams of phenolic resin (containing 1% gamma-aminopropyl-triethoxy-silane in resin) is added to after 200 DEG C and is stirred 45 seconds, added
(hexamethylenetetramine is 1 with the mass ratio of water to hexamethylenetetramine aqueous solution:2) 27 grams and stir solidification 140 seconds;Cool to
26.3 grams of the sulfonate polyester polyol of the preparation of embodiment 2 is added after 140 DEG C and is stirred 30 seconds, add 75 grams of hydrogel dry powder to stir
Mix 50 seconds, add 3.8 grams of stirring solidifications of polymethylene multi-phenenyl isocyanate (PM-200), until granule is completely dispersed, cooling,
Sieve, obtain the present invention can suspended prop.
Embodiment 8 (comparative example)
After 3 kilograms of particle diameters are heated to into 220 DEG C for the low close haydite same as Example 7 of 850/425 μm (20/40 mesh)
It is put in self-control puddle mixer and stirs, 26.3 grams of the sulfonate polyester polyol of the preparation of embodiment 2 is added after being cooled to 140 DEG C and is stirred
Mix 40 seconds, add 75 grams of hydrogel dry powder to stir 50 seconds, add 3.8 grams of stirrings of polymethylene multi-phenenyl isocyanate (PM-200)
Solidification, until granule is completely dispersed, cools down, sieves, and obtains contrasting proppant.
Embodiment 9 (comparative example)
After 3 kilograms of particle diameters are heated to into 220 DEG C for the low close haydite same as Example 7 of 850/425 μm (20/40 mesh)
It is put in self-control puddle mixer and stirs, 26.8 grams of epoxy resin is added after being cooled to 200 DEG C and is stirred 50 seconds, adds hydrogel dry powder
75 grams are stirred 50 seconds, add 3.2 grams of stirring solidifications of diaminodiphenyl-methane, until granule is completely dispersed, is cooled down, are sieved, and are obtained
To contrast proppant.
The embodiment 7,8 of table 2. and 9 Comparative results
Note:150ml beakers add 20 grams of proppants, plus 100ml water, observation proppant expansion multiple and shelling phenomenon
Embodiment 10
By low close haydite (the prosperous high-tech of the Pingxiang City hundred million ceramics company limited that 3 kilograms of particle diameters are 425/212 μm (40/70 mesh)
Production, bulk density 1.18g/cm3, apparent density 2.23g/cm3) be heated to 230 DEG C after be put into self-control puddle mixer in stir, cooling
75 grams of phenolic resin (containing 0.5% gamma-aminopropyl-triethoxy-silane in resin) is added to after 210 DEG C and is stirred 50 seconds, plus
(hexamethylenetetramine is 1 with the mass ratio of water to enter hexamethylenetetramine aqueous solution:2) 34 grams and stir solidification 120 seconds;Cool to
26.5 grams of the sulfonate polyester of the preparation of embodiment 3 is added after 140 DEG C and is stirred 40 seconds, add the 75 grams of stirrings 50 of hydrogel dry powder
Second, 3.5 grams of stirring solidifications of polymethylene multi-phenenyl isocyanate (PM-200) are added, until granule is completely dispersed, cooling, mistake
Sieve, obtain the present invention can suspended prop.
Embodiment 11 (comparative example)
Put after 3 kilograms of particle diameters are heated to into 220 DEG C for 425/212 μm of (40/70 mesh) low close haydite same as Example 8
Enter to make by oneself in puddle mixer and stir, 26.5 grams of the sulfonate polyester polyol of the preparation of embodiment 3 is added after being cooled to 140 DEG C and is stirred
40 seconds, add 75 grams of hydrogel dry powder to stir 50 seconds, add 3.5 grams of stirrings of polymethylene multi-phenenyl isocyanate (PM-200) solid
Change, until granule is completely dispersed, cools down, sieve, obtain contrasting proppant.
The embodiment 10 of table 3. and 11 Comparative results
Note:150ml beakers add 20 grams of proppants, plus 100ml water, observation proppant expansion multiple and shelling phenomenon
Can hydrogel degradation experiment on suspended prop
70 DEG C of degradeds:The proppant that embodiment 4-11 is respectively put in 150 milliliters of beaker is each 30 grams, and addition contains
The tap water of 0.06 weight % Ammonium persulfate. is each 100 grams, is put in 70 DEG C of waters bath with thermostatic control and is incubated, the water in rear support agent in 4 hours
Gel is all degraded.
50 DEG C of degradeds:The proppant that embodiment 4-11 is respectively put in 150 milliliters of beaker is each 30 grams, and addition contains
100 grams of the tap water of 0.03 weight % Ammonium persulfate. and 0.03 weight % Potassium metaperiodate., is put in 50 DEG C of waters bath with thermostatic control and is incubated, and 12
Hydrogel in hour rear support agent is all degraded.