CN100469717C

CN100469717C - Treatment method for recovering inverted discharged pressing crack liquid

Info

Publication number: CN100469717C
Application number: CNB200610010499XA
Authority: CN
Inventors: 冯久志
Original assignee: Individual
Current assignee: Individual
Priority date: 2006-09-06
Filing date: 2006-09-06
Publication date: 2009-03-18
Anticipated expiration: 2026-09-06
Also published as: CN1915867A

Abstract

This invention relates to a method for recovering and treating fracturing fluid to solve the problem of fracturing fluid pollution. The method comprises: (1) adding a gel breaker to the fracturing fluid for gel breaking; (2) adding flocculants for flocculation; (3) oxidizing after flocculation; (4) secondarily flocculating after oxidization; (5) secondarily oxidizing after secondary flocculation. The treated fracturing fluid can satisfy national second-class standards for discharging or refluxing.

Description

Treatment method for recovering inverted discharged pressing crack liquid

Technical field:

The present invention relates to anti-discharge opeing recovery processing technique in the oil-gas field field, especially a kind of treatment method for recovering inverted discharged pressing crack liquid.

Background technology:

Present fast development along with national economy; demand to petrochemicals is more and more; also environment protection is more and more paid attention to simultaneously, the annual inverted discharged pressing crack liquid of Daqing Area effluxes 3～5 ten thousand steres at least, the pollution that the objectionable impurities in the anti-discharge opeing is serious environment.The fracturing liquid prescription mainly is to classify by the adaptability of different rocks, and the fracturing liquid composition can be divided into three major types: water base, oil base, emulsification fracturing liquid.On these three kinds of of the fracturing fluid bases,, every kind of fracturing liquid can be divided into shallow well, middle-deep well, deep well fracturing liquid in order to adapt to the needs of different well depths.More than several of the fracturing fluid basic binder components be: (viscosifying agent is hydroxypropyl guanidine glue (Guar to guanidine glue; Gum Cyanopsis), be called for short guanidine glue, molecular weight is about 220000, and its proterties is natural nonionic glycan), clay stabilizer, sterilant, defoamer, organic borate cross-linker, high-temperature cross-linking agent, cleanup additive.

According to Different Strata structure and bottom temperature, mainly be that the different proportionings by above additive are configured fracturing liquid, but essentially consist is constant.Wherein the emulsification fracturing liquid is mainly used in the exploratory area, Hailaer, has added a kind of emulsifying agent in the component more, other component basically identicals.Fracturing liquid also can be classified by the temperature difference, is divided into 140 ℃, and 90 ℃ and 70 ℃ of three kinds of fracturing liquids are selected the fracturing liquid of differing temps for use according to the temperature difference on stratum.Main additive wherein has: cleanup additive, expansion-resisting agent, sterilant, high-temperature cross-linking agent, organic borate cross-linker and gel breaker.For the fracturing liquid of differing temps, mainly be to reach variation on the temperature by the adding proportion that changes above additive.

Summary of the invention:

In order to overcome disadvantages of background technology, the invention provides treatment method for recovering inverted discharged pressing crack liquid, the inverted discharged pressing crack liquid of crossing through this art breading reaches the purpose of national secondary discharge standard or re-injection.

Technical scheme of the present invention is: this treatment method for recovering inverted discharged pressing crack liquid is characterized in that: comprise the following steps:

(1) at first in inverted discharged pressing crack liquid, adds gel breaker and break glue;

(2) add flocculation agent behind the broken glue of inverted discharged pressing crack liquid and flocculate, the add-on of PA flocculation agent and ZN-1 coagulant aids is respectively 3000PPm and 50PPm, reaction times 30min;

(3) carry out oxidation after the flocculation, adding SYJ-2 oxidant hydrogen peroxide input amount during oxidation is 1.5%, and the reaction times is 3h;

(4) carry out the secondary flocculation after the oxidation again, PA flocculation agent and ZN-1 coagulant aids input amount are respectively 1500PPm and 30PPm, and the reaction times is 30min;

(5) carry out secondary oxidation after the flocculation, add RYJ-1 oxygenant dioxide peroxide, for input amount is 2000PPm, the reaction times is 4h.

The present invention has following beneficial effect: the present invention is directed to the inverted discharged pressing crack liquid particular case, implemented above-mentioned processing step, the COD value is reduced to 91mg/L, pH value 7.5, the total chromium 0.05mg/L of colourity/multiple, suspended substance 5mg/L in the waste liquid after treatment, has reached fully to efflux or the re-injection requirement.The treatment temp of each technique unit is normal temperature, does not need heat treated.

Description of drawings:

Fig. 1 oxidization time and COD clearance relation curve;

The oxidization time of Fig. 2 strong oxidizer RYJ-1 and COD clearance relation curve;

Fig. 3 is a process flow sheet of the present invention.

Embodiment:

The invention will be further described below in conjunction with embodiment:

The used base fluid of the present invention is collected in that second oil recovery factory south 256-is oblique 272, southern 248-is oblique 254, the oblique 260 3 mouthfuls of anti-removal waste fluids of fractured well of southern 198-, be broken glue after, gel breaker is a Potassium Persulphate, dosage is 0.4%, numbers to be respectively 1,2, No. 3.

To the in office analysis of carrying out behind the broken glue of waste liquid, analytical results sees the following form

Table 1

Index	CODcr mg/L	hH	Colourity/multiple	Total chromium mg/L	SS mg/L
Index	CODcr mg/L	hH	Colourity/multiple	Total chromium mg/L	SS mg/L	Country's secondary discharge standard (petrochemical complex)	<120	6～9	<80	<1.5	<150
No. 1 water sample	4389	7.5	324	0.85	736		<120	6～9	<80	<1.5	<150
No. 1 water sample	4389	7.5	324	0.85	736	No. 2 water samples	3991	7.2	286	0.53	569
No. 3 water samples	3829	7.3	309	0.46	764	No. 2 water samples	3991	7.2	286	0.53	569
No. 3 water samples	3829	7.3	309	0.46	764	Mean value	4069.6	7.33	306.33	0.613	689.23

Three every data differences of water sample are little as can be seen by table 1 data analysis.

Below the above-mentioned water sample chamber of experimentizing is tested:

Experiment and analytical instrument: flocculating experiment device; 722 spectrophotometers; COD _GrAnd Measuring apparatus; Aerating apparatus; Whipping appts; Ten thousand/analytical balance.

Experimental drug product: SYJ-2 type oxygenant; RYJ-1 type oxygenant; Gel breaker; PA type flocculant poly aluminium chloride ferrum is called for short compound ferro-aluminum PAFC; ZN-1 type coagulant aids polyacrylamide (molecular weight is between 1,400,000 to 1,600,000); Measure CO D _CrAnd

Used chemical reagent.

One, determining of flocculation agent addition: the best dosage data of flocculation agent see the following form 2.

Table 2

Added amount of chemical	Phenomenon	CODcr mg/L	Colourity/multiple	Color
Added amount of chemical	Phenomenon	CODcr mg/L	Colourity/multiple	Color	No. 1, waste liquid		4389	324	Tawny
PA flocculation agent 1000PPm+ 20PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	2697	294	Yellow	No. 1, waste liquid		4389	324	Tawny
PA flocculation agent 1000PPm+ 20PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	2697	294	Yellow	PA flocculation agent 1500PPm+ 30PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	2015	236	Yellow
PA flocculation agent 2000PPm+ 40PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	1820	156	Faint yellow	PA flocculation agent 1500PPm+ 30PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	2015	236	Yellow
PA flocculation agent 2000PPm+ 40PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	1820	156	Faint yellow	PA flocculation agent 2500PPm+ 45PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	821	146	Faint yellow
PA flocculation agent 3000PPm+ 50PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	560	50	As clear as crystal	PA flocculation agent 2500PPm+ 45PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	821	146	Faint yellow
PA flocculation agent 3000PPm+ 50PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	560	50	As clear as crystal	PA flocculation agent 3500PPm+ 60PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	556	45	As clear as crystal
PA flocculation agent 1000PPm+ 20PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	550	45	As clear as crystal	PA flocculation agent 3500PPm+ 60PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	556	45	As clear as crystal

By table 2 data as can be seen PA flocculation agent and the only dosage of ZN-1 coagulant aids be 3000PPm and 50PPm, can reach about 90% the clearance of COD.

Two, determining of once oxidation YJ-2 type oxygenant dosage, best dosage of YJ-2 type oxygenant and COD clearance data see the following form 3:

Table 3

Oxidization time 3h as can be seen from Table 3, the best dosage of SYJ-2 type oxygenant is 1.5%, is about 60% to the clearance of COD.Relation between oxidization time and the COD clearance is illustrated in fig. 1 shown below: the SYJ-2 dosage is 1.5% as seen from Figure 1, and the oxidization time oxidization time is 2～3h best results.

Three, can reduce to about 220 through COD value after broken glue, flocculation, the oxidation for the first time and continue to add flocculation agent and coagulant aids the results are shown in following table 4.

Table 4

Added amount of chemical	Phenomenon	CODcr mg/L	CODcr clearance %	Colourity/multiple	Color
Added amount of chemical	Phenomenon	CODcr mg/L	CODcr clearance %	Colourity/multiple	Color	No. 1, waste liquid		220		50	As clear as crystal
PA flocculation agent 1000PPm+ 20PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	172	21.82	30	As clear as crystal	No. 1, waste liquid		220		50	As clear as crystal
PA flocculation agent 1000PPm+ 20PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	172	21.82	30	As clear as crystal	PA flocculation agent 1500PPm+ 30PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	156	29.09	25	As clear as crystal
PA flocculation agent 2000PPm+ 40PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	152	30.91	25	As clear as crystal	PA flocculation agent 1500PPm+ 30PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	156	29.09	25	As clear as crystal
PA flocculation agent 2000PPm+ 40PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	152	30.91	25	As clear as crystal	PA flocculation agent 2500PPm+ 45PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	150	31.82	25	As clear as crystal
PA flocculation agent 3000PPm+ 50PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	150	31.82	25	As clear as crystal	PA flocculation agent 2500PPm+ 45PPmZN-1 coagulant aids	Flco is big, sedimentation is fast	150	31.82	25	As clear as crystal

By last table 4 as can be seen the best dosage of PA flocculation agent and ZN-1 coagulant aids be 1500PPm and 30PPm, the clearance of COD can reach about 30%.

Four, through after the above processing, the COD value in the waste liquid mainly is that the material by some small molecules difficult degradations forms, and post-processed must the stronger oxygenant of usefulness, and RYJ-1 type oxygenant is a kind of superpower oxygenant, adds concentration and oxidization time is as shown in table 5 below:

Table 5

By last table 5 as can be seen the best dosage of strong oxidizer RYJ-1 be 2000PPm, oxidization time is 4h.The oxidization time of strong oxidizer RYJ-1 and COD clearance relation curve are illustrated in fig. 2 shown below: oxidization time 4 ~ 5h can reach best effect as seen from Figure 2.

Draw treatment process condition by above-mentioned experiment:

The treatment temp of each technique unit is normal temperature, does not need heat treated;

1, once flocculation adds medicament PA flocculation agent and the ZN-1 coagulant aids is divided into 3000PPm and 50PPm, reaction times 30min.

2, to add medicament SYJ-2 oxidant hydrogen peroxide be to be 3h in 1.5% reaction times to once oxidation.

3, secondary flocculation adds medicament PA flocculation agent and the ZN-1 coagulant aids is respectively 1500PPm and 30PPm, and the reaction times is 30min.

4, to add medicament RYJ-1 dioxide peroxide be 2000PPm to secondary oxidation, and the reaction times is 4h.

The COD value is reduced to 91mg/L, pH value 7.5, colourity/multiple 25, total chromium 0.05mg/L, suspended substance 5mg/L in the waste liquid after treatment, has reached fully to efflux or the re-injection requirement.

Five, waste liquid check after above-mentioned steps is handled, detect (GB11914-89) and " the mensuration potassiumiodide basic potassium permanganate method of chemical oxygen demand of high-chloride wastewater " (HJ132-2003) standard, every index such as following table 6 according to " the mensuration potassium dichromate process of hydrochemistry oxygen requirement ".

Table 6

Index	CODcr mg/L	pH	Colourity/multiple	Total chromium mg/L	SS mg/L
Index	CODcr mg/L	pH	Colourity/multiple	Total chromium mg/L	SS mg/L	Country's secondary discharge standard (petrochemical complex)	<120	6～9	<80	<1.5	<150
No. 1 water sample	91	7.5	25	0.05	5		<120	6～9	<80	<1.5	<150

By above each data as can be seen,, can remove the COD in the anti-removal waste fluid effectively, reach the purpose of national secondary discharge standard discharging or re-injection with after flocculation-oxidation-flocculation-oxidation.

Claims

1, a kind of treatment method for recovering inverted discharged pressing crack liquid is characterized in that: comprise the following steps:

(2) add flocculation agent behind the broken glue of inverted discharged pressing crack liquid and flocculate, the add-on of flocculant poly aluminium chloride ferrum and coagulant aids polyacrylamide is respectively 3000PPm and 50PPm, reaction times 30min;

(3) carry out oxidation after the flocculation, adding the oxidant hydrogen peroxide input amount during oxidation is 1.5%, and the reaction times is 3h;

(4) carry out the secondary flocculation after the oxidation again, flocculation agent and coagulant aids input amount are respectively 1500PPm and 30PPm, and the reaction times is 30min;

(5) carry out secondary oxidation after the flocculation, add the oxygenant dioxide peroxide, for input amount is 2000PPm, the reaction times is 4h.