CN106145296A - A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment - Google Patents

A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment Download PDF

Info

Publication number
CN106145296A
CN106145296A CN201610778042.7A CN201610778042A CN106145296A CN 106145296 A CN106145296 A CN 106145296A CN 201610778042 A CN201610778042 A CN 201610778042A CN 106145296 A CN106145296 A CN 106145296A
Authority
CN
China
Prior art keywords
flocculant
weight portion
flocculation agent
treatment
outlet liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610778042.7A
Other languages
Chinese (zh)
Inventor
鲍晋
何启平
尹丛彬
陆丽
蔡远红
周瀚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNPC Chuanqing Drilling Engineering Co Ltd
Original Assignee
CNPC Chuanqing Drilling Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CNPC Chuanqing Drilling Engineering Co Ltd filed Critical CNPC Chuanqing Drilling Engineering Co Ltd
Priority to CN201610778042.7A priority Critical patent/CN106145296A/en
Publication of CN106145296A publication Critical patent/CN106145296A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Abstract

The invention discloses a kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment, comprising: (1) gets the raw materials ready: high viscosity biological flocculant 0.5 ~ 1 weight portion；Aluminium polychlorid 1.5 ~ 3 weight portion；Anhydrous citric acid 10 ~ 30 weight portion；Tap water 1000 weight portion；(2) preparing: first add to be added by citric acid in 500 weight portion tap waters and stir, regulation system pH is 2 ~ 3, is subsequently adding high viscosity biological flocculant, and flocculant 1# is made in stirring；Being added by aluminium polychlorid in remaining 500 weight portion tap waters again, flocculant 2# is made in stirring.Use this method, solve the own difficult degradation now generally existed with shale gas fracturing outlet liquid flocculation treatment agent and can cause secondary pollution or the problem that fracturing fluid property is affected greatly by high volence metal ion can be introduced.

Description

A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment
Technical field
The present invention relates to shale gas fracturing outlet liquid reuse pre-treatment flocculant technical field.
Background technology
China's shale gas exploits great-leap-forward development to be realized, and Water Resources Pressure is big, with the shale gas pressure break of Weiyuan, Changning is Example, about 2014 ~ 2015 years needs dosing use water 2,680,000 sides, leads calculating by the row of returning of 30% ~ 50%, and the waste liquid of the row of returning 80.4 ~ 1340000 sides.Therefore, the large-scale fracturing freshwater resources build-up of pressure to China's shortage.Existing development block environment pole It is sensitive, and ecological environmental protection requires height, and China's shale gas resource-rich regions much concentrates on mountainous region in middle and western China, ground, south, existing another name for Sichuan Province The shale gas zones and surface areas for joint exploration and exploitation such as head of district Ning-Weiyuan, all in Farmland, earth's surface is with a varied topography, densely populated.Therefore, return discharge opeing to return Be alleviate environmental protection pressure, reduce production cost effective way.
But, return discharge opeing and contain a large amount of solid suspension insoluble matter；There is the phenomenon of " turning black smelly " in long storage time；Turbidity High (150 ~ 250NTU)；COD is high (500 ~ 2000mg/L)；Salinity is high (10000 ~ 20000mg/L), and Ca2+、Mg2+Deng two The above metal ion content of valency is more.Direct reuse can cause water quality to deteriorate further, not only can damage reservoir, impact The property indices of fracturing fluid, also can increase environmental risk.So, before returning discharge opeing reuse, it is necessary to process.
Find conventional flocculant such as polyacrylamide (PAM) by substantial amounts of experiment, it will be made effectively to process shale Gas fracturing outlet liquid, it is desirable to its molecular weight is more than 18,000,000, for the PAM of molecular weight more than 18,000,000, itself difficult degradation Secondary pollution can be caused；And the conventional flocculant poly aluminum chloride (PAC) of another kind can introduce high volence metal ion to pressure break fluidity Can affect greatly, field integrated using effect is the most undesirable.
Summary of the invention
It is contemplated that for the defect existing for above-mentioned prior art and deficiency, it is provided that a kind of fracturing outlet liquid that is used for returns By the composite flocculation agent preparation method of pre-treatment, use this method, solve existing shale gas fracturing outlet liquid flocculation treatment agent The own difficult degradation generally existed can cause secondary pollution or can introduce high volence metal ion and cause fracturing fluid property bigger The problem of impact.
The present invention realizes by using following technical proposals:
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment, it is characterised in that:
(1) get the raw materials ready: high viscosity biological flocculant 0.5 ~ 1 weight portion；Aluminium polychlorid 1.5 ~ 3 weight portion；Anhydrous citric acid 10 ~ 30 Weight portion；Tap water 1000 weight portion；
(2) preparing: first add to be added by citric acid in 500 weight portion tap waters and stir, regulation system pH is 2 ~ 3, then adds Entering high viscosity biological flocculant, flocculant 1# is made in stirring；Aluminium polychlorid is added remaining 500 weight portion tap waters again In, flocculant 2# is made in stirring.
The using method of this composite flocculation agent is, flocculant 1#, 2# is added with effective concentration 2mg/L, 5mg/L respectively Enter in pending fracturing fluid recovery (backflow) liquid, stir the rotating speed stirring 14min of 1min, 60rpm with the rotating speed of 250rpm, stand 15min。
It is modified β-Isosorbide-5-Nitrae-poly-D-glucosamine that described height glues biological flocculant, uses acrylamide to deacetylated Degree >=95%, the β-1,4-poly-D-glucosamine modification of viscosity >=400mPa.s.
The method of modifying of the poly-D-glucosamine of β-1,4-is: takes the 1 weight portion poly-D-glucosamine of β-1,4-and dissolves Being the acetum of 1% in mass fraction, be placed in the four-hole boiling flask with agitating device, at 40 DEG C of constant temperature water baths, nitrogen is protected Protect down, add people's initiator, stir 15min；It is warming up to 45 DEG C, is slowly added dropwise the aqueous solution containing 5 parts by weight propylene amide monomers, Reaction 3h, is transferred out reactant；Product is poured in acetone, make graft copolymer precipitant separate out, after decompression sucking filtration, vacuum It is dried to constant weight.
Described initiator be concentration be the ceric ammonium nitrate solution of 1mmol/L.
Flocculant 1# is made in described stirring, is to stir 1min with the rotating speed of 300rpm, makes flocculant 1#.
Flocculant 2# is made in described stirring, is to stir 1min with the rotating speed of 200rpm, makes flocculant 2#.
Compared with prior art, what the present invention was reached has the beneficial effect that:
1, the poly-D-glucosamine of high viscosity biological flocculant modification β-1,4-is to be taken off through a series of chemical treatments by chitin The molecular weight obtained after acetyl group is the product of the biomacromolecule of 12-59 ten thousand, re-uses acrylic amide modified, strengthens its flocculation Effect；There is flocculability good, nontoxic as water treatment agent or the advantage such as low toxicity, strong, the non-secondary pollution of absorption sequestering power, but High deacetylized biological flocculant shale gas fracturing outlet liquid being had to preferable flocculating effect is relatively costly.The present invention passes through Substantial amounts of experimental studies have found that specific high viscosity biological flocculant and aluminium polychlorid are with the ratio of this programme and processing routine at Reason shale gas fracturing outlet liquid, not only can obtain good flocculating effect, greatly reduce the consumption of biological flocculant, and The chelation of biological flocculant just can remove the aluminium ion that aluminium polychlorid introduces completely, will not be to the performance of fracturing fluid Have undesirable effect.
2, verifying through embodiment part Experiment, this composite flocculation agent has the highest good flocculating effect (turbidity removal rate 95% Above, COD clearance more than 75%, total ferrum clearance more than 95%, Ca2+、Mg2+Clearance more than 30%), can effectively solve long-term The problem storing " turning black smelly "；Itself is degradable does not results in secondary pollution；High volence metal ion will not be introduced to fracturing fluid Performance have undesirable effect.
Detailed description of the invention
Embodiment 1:
As the preferred forms of the present invention, its scheme is as follows: the key component height of composite flocculation agent glues biological flocculant generation Number HVCAM its preparation method is: take 1g deacetylation >=95%, viscosity >=400mPa.s the poly-D-glucosamine of β-1,4-molten Solution is the acetum of 1% in mass fraction, is placed in the four-hole boiling flask with agitating device, at 40 DEG C of constant temperature water baths, nitrogen Under protection, add people's initiator ceric ammonium nitrate solution (1mmol/L), stir 15min.It is warming up to 45 DEG C, is slowly added dropwise containing 5g third The aqueous solution of acrylamide monomer, reacts 3h, is transferred out reactant.Product is poured in acetone, make graft copolymer precipitant Separate out, after decompression sucking filtration, be dried under vacuum to constant weight.
The compound method of this composite flocculation agent is: first adds and will stir under citric acid 10 ~ 30g addition 500g tap water, Regulation system pH is 2 ~ 3, is subsequently adding high viscosity biological flocculant 0.5 ~ 1g and stirs 1min with the rotating speed of 300rpm, makes flocculation Agent 1#；Again aluminium polychlorid 1.5 ~ 3g is added in remaining 500g tap water, stir 1min with the rotating speed of 200rpm, make wadding Solidifying agent 2#.
The preparation using method of this composite flocculation agent: by flocculant 1#, 2# respectively with effective concentration 2mg/L, 5mg/L Add in pending fracturing fluid recovery (backflow) liquid, stir the rotating speed stirring 14min of 1min, 60rpm with the rotating speed of 250rpm, stand 15min。
The key component height of this composite flocculation agent glues biological flocculant code name HVCAM for modified β-1,4-poly-D-amino Portugal Grape sugar, uses acrylamide modified to the β-Isosorbide-5-Nitrae-poly-D-glucosamine of deacetylation >=95%, viscosity >=400mPa.s, its Method of modifying is: takes 1 weight portion β-Isosorbide-5-Nitrae-poly-D-glucosamine and is dissolved in the acetum that mass fraction is 1%, is placed in band Have in the four-hole boiling flask of agitating device, under 40 DEG C of constant temperature water baths, nitrogen protection, add people's initiator ceric ammonium nitrate solution (1mmol/L), stirring 15min.It is warming up to 45 DEG C, is slowly added dropwise the aqueous solution containing 5 parts by weight propylene amide monomers, reaction 3h, is transferred out reactant.Product is poured in acetone, make graft copolymer precipitant separate out, after decompression sucking filtration, vacuum drying To constant weight.
The preparation raw material of high viscosity biological flocculant code name HVCAM, aluminium polychlorid code name PAC, anhydrous citric acid code name CA is on market sale product, and strictly by industry standard or enterprise's mark inspection when purchasing, eligible could use, and is specifically shown in Table 1:
Embodiment 2:
According to the preparation method of embodiment 1, prepare composite flocculation agent 1#, 2#, and according to stone in the using method process of embodiment 1 Oil Weiyuan 204-H6 shale gas platform fracturing outlet liquid.Water quality contrast before and after process is shown in Table 2:
Embodiment 3
As another better embodiment of the present invention, its preparation method is as follows:
(1) get the raw materials ready: high viscosity biological flocculant 0.5 weight portion；Aluminium polychlorid 1.5 weight portion；Anhydrous citric acid 10 weight portion； Tap water 1000 weight portion；
(2) preparing: first add to be added by citric acid in 500 weight portion tap waters and stir, regulation system pH is 2, is subsequently adding High viscosity biological flocculant, flocculant 1# is made in stirring；Again aluminium polychlorid is added in remaining 500 weight portion tap waters, Flocculant 2# is made in stirring.
Embodiment 4
As another better embodiment of the present invention, its preparation method is as follows:
(1) get the raw materials ready: high viscosity biological flocculant 1 weight portion；Aluminium polychlorid 3 weight portion；Anhydrous citric acid 30 weight portion；From the beginning Water 1000 weight portion；
(2) preparing: first add to be added by citric acid in 500 weight portion tap waters and stir, regulation system pH is 3, is subsequently adding High viscosity biological flocculant, flocculant 1# is made in stirring；Again aluminium polychlorid is added in remaining 500 weight portion tap waters, Flocculant 2# is made in stirring.
Embodiment 5
As an also better embodiment of the present invention, high viscous biological flocculant is modified β-Isosorbide-5-Nitrae-poly-D-glucosamine, makes Modified to the poly-D-glucosamine of β-1,4-of deacetylation >=95%, viscosity >=400mPa.s with acrylamide.β-1,4-is poly- The method of modifying of D-glucosamine is: taking the 1 weight portion poly-D-glucosamine of β-1,4-and being dissolved in mass fraction is 1% Acetum, is placed in the four-hole boiling flask with agitating device, under 40 DEG C of constant temperature water baths, nitrogen protection, adds people's initiator, stirs Mix 15min；It is warming up to 45 DEG C, is slowly added dropwise the aqueous solution containing 5 parts by weight propylene amide monomers, react 3h, be transferred out reaction Thing；Product is poured in acetone, make graft copolymer precipitant separate out, after decompression sucking filtration, be dried under vacuum to constant weight.Described Initiator be concentration be the ceric ammonium nitrate solution of 1mmol/L.

Claims (7)

1. the composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment, it is characterised in that:
(1) get the raw materials ready: high viscosity biological flocculant 0.5 ~ 1 weight portion；Aluminium polychlorid 1.5 ~ 3 weight portion；Anhydrous citric acid 10 ~ 30 Weight portion；Tap water 1000 weight portion；
(2) preparing: first add to be added by citric acid in 500 weight portion tap waters and stir, regulation system pH is 2 ~ 3, then adds Entering high viscosity biological flocculant, flocculant 1# is made in stirring；Aluminium polychlorid is added remaining 500 weight portion tap waters again In, flocculant 2# is made in stirring.
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment the most according to claim 1, its It is characterised by: the using method of this composite flocculation agent is, by flocculant 1#, 2# respectively with effective concentration 2mg/L, 5mg/L Add in pending fracturing fluid recovery (backflow) liquid, stir the rotating speed stirring 14min of 1min, 60rpm with the rotating speed of 250rpm, stand 15min。
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment the most according to claim 1, its It is characterised by: it is modified β-Isosorbide-5-Nitrae-poly-D-glucosamine that described height glues biological flocculant, uses acrylamide to deacetylated Degree >=95%, the β-1,4-poly-D-glucosamine modification of viscosity >=400mPa.s.
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment the most according to claim 3, its It is characterised by: the method for modifying of the poly-D-glucosamine of β-1,4-is: take the 1 weight portion poly-D-glucosamine of β-1,4-and dissolve Being the acetum of 1% in mass fraction, be placed in the four-hole boiling flask with agitating device, at 40 DEG C of constant temperature water baths, nitrogen is protected Protect down, add people's initiator, stir 15min；It is warming up to 45 DEG C, is slowly added dropwise the aqueous solution containing 5 parts by weight propylene amide monomers, Reaction 3h, is transferred out reactant；Product is poured in acetone, make graft copolymer precipitant separate out, after decompression sucking filtration, vacuum It is dried to constant weight.
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment the most according to claim 4, its Be characterised by: described initiator be concentration be the ceric ammonium nitrate solution of 1mmol/L.
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment the most according to claim 1, its It is characterised by: flocculant 1# is made in described stirring, is to stir 1min with the rotating speed of 300rpm, makes flocculant 1#.
A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment the most according to claim 1, its It is characterised by: flocculant 2# is made in described stirring, is to stir 1min with the rotating speed of 200rpm, makes flocculant 2#.
CN201610778042.7A 2016-08-31 2016-08-31 A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment Pending CN106145296A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610778042.7A CN106145296A (en) 2016-08-31 2016-08-31 A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610778042.7A CN106145296A (en) 2016-08-31 2016-08-31 A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment

Publications (1)

Publication Number Publication Date
CN106145296A true CN106145296A (en) 2016-11-23

Family

ID=57344985

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610778042.7A Pending CN106145296A (en) 2016-08-31 2016-08-31 A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment

Country Status (1)

Country Link
CN (1) CN106145296A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109160691A (en) * 2018-10-09 2019-01-08 中国石油集团川庆钻探工程有限公司 A kind of shale gas fracturing outlet liquid processing method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302273A (en) * 2008-06-30 2008-11-12 重庆大学 Preparation of chitose-acrylic amide graft copolymerization flocculant
CN102351343A (en) * 2011-07-08 2012-02-15 南开大学 Method for effectively removing residual aluminum in water by adopting flocculation process
CN104284866A (en) * 2012-03-28 2015-01-14 哈洛资源公司 Water treatment compositions and methods of use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302273A (en) * 2008-06-30 2008-11-12 重庆大学 Preparation of chitose-acrylic amide graft copolymerization flocculant
CN102351343A (en) * 2011-07-08 2012-02-15 南开大学 Method for effectively removing residual aluminum in water by adopting flocculation process
CN104284866A (en) * 2012-03-28 2015-01-14 哈洛资源公司 Water treatment compositions and methods of use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109160691A (en) * 2018-10-09 2019-01-08 中国石油集团川庆钻探工程有限公司 A kind of shale gas fracturing outlet liquid processing method

Similar Documents

Publication Publication Date Title
Ren et al. Efficient removal of phosphorus from turbid water using chemical sedimentation by FeCl3 in conjunction with a starch-based flocculant
JPH08165B2 (en) Composition and method for condensing and removing solids suspended in water
CN104724809B (en) A kind of ternary polymerization flocculant based on natural polymer and preparation method thereof
CN104445563B (en) A kind of macromolecule heavy metal flocculant and preparation method thereof
CN106459312B (en) The method that the water slurry of solid particle is handled using comb polymer
CN105129944A (en) Inorganic and modified chitosan composite polymer flocculant
CN104071962A (en) Treatment method of river or lake sediments
CN101921015B (en) Novel inorganic-organic composite macromolecular decolorizing flocculant and preparation method thereof
CN108314759A (en) A kind of chitin modified preparation method except alga flocculating agent
CN101307119A (en) Method for preparing amphiprotic chitosan flocculant
CN105540804A (en) Method for using camellia oleifera extract product for preparing cationic flocculant
CN102863059A (en) Additive for enhancing function of organism in aspect of ammonia nitrogen removal in water and use method of additive
CN107011471A (en) A kind of preparation method of Instant high molecular weight polyacrylamide
CN105524220A (en) Method for preparing chitosan-modified polymeric flocculant
CN103864190A (en) Multifunctional water purifier and preparation method thereof
CN106145296A (en) A kind of composite flocculation agent preparation method for fracturing outlet liquid reuse pre-treatment
CN105600898B (en) A kind of preparation method of purifying sea water flocculant and obtained flocculant
CN105440225A (en) Preparation method of polyphenol biomass flocculating agent
CN104030421B (en) A kind of compound COD remover and waste water COD minimizing technology thereof
CN102408145A (en) Composite flocculant and use thereof
CN106241983A (en) A kind of purification process technique of waste or used plastics wash water
CN106830122A (en) Removal heavy metal in waste water inorganic agent
CN103524640A (en) Preparation method of water soluble N-carboxyethyl chitosan
CN110002562A (en) A kind of sea grass polysaccharide flocculation aid and the preparation method and application thereof
CN105664417A (en) Heavy metal chelating agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20161123

RJ01 Rejection of invention patent application after publication