A kind of degreaser of heavy crude heat extraction sewage and preparation method thereof
Technical field
The present invention relates to a kind of degreasers of disposing polluted water in oil, and the oil removing of sewage disposal is gone out especially suitable for heavy crude heat extraction
Agent.
Background technology
The viscosity of viscous crude is big, and the sewage disposal for exploiting generation is always to restrict one of the important link of its development.Crude oil passes through
After the heat chemistry settling processing a period of time for crossing dehydration, silt and other mechanical admixtures enter sewerage together, make dirt
Total suspended matter in water reaches 20000mg/L or so.Larger difficulty is caused to sewage disposal.Meanwhile in order to enable super-viscous oil
Ground is given rise to, the substances such as some surfactants, such as sulfonate are added in oil recovery process so that Produced Liquid needs
Breaking emulsion and dewatering causes a large amount of chemical agent to remain in sewage, and causing sewage, not only oil content is high, but also the stabilization of emulsion
Property is strong so that sewage oil removing and purified treatment are increasingly complex.
Conventional treatment process (natural subsidence-coagulant precipitation-filtering) is difficult that heavy crude heat extraction sewage is made to obtain effectively at present
Processing.Another method for removing oil-bearing wastewater Crude Oil is chemical method, that is, uses oil removing agent method.Degreaser substantially divides
For following two categories, the element of the first species is various, and deoiling effect is good, but that there is preparation processes is complicated, anti-salt property is poor, cost is higher
Disadvantage;Another kind of degreaser ingredient is single, and preparation method and technique are relatively simple, and the requirement to water quality is relatively low, but exists and remove
The disadvantage of oily effect difference.It is less for the patent in terms of condensed oil sewage processing at present.
Patent ZL201410254042.8 " a kind of composite flocculation deoiling agent for oily waste water treatment " uses sulfuric acid
Aluminium, magnesium chloride, magnesium hydroxide, bentonite and polyacrylamide are combined, which has dosage few, and oil removal efficiency is high,
Prepare it is simple, it is at low cost the features such as, but degreaser needs are used with corrosive magnesium hydroxide, and the compound is to equipment
With stronger corrosiveness.
Invention content
The present invention is directed to the problems such as undesirable currently used for heavy crude heat extraction sewage deoiling effect, and proposes a kind of technique letter
Single, of low cost, heat-resistant salt-resistant, and the degreaser for being suitable for heavy crude heat extraction sewage processing that deoiling effect is good.
The invention discloses a kind of degreaser of heavy crude heat extraction sewage, which is by acrylamide, N- benzyl-N- second
Base acrylamide and vinyl acetate are made by micellar free radical copolymerization method, and molecular weight is 6000~50000, molecular formula
It is as follows:
M=40~340, preferably 120~180;
N=2~250, preferably 30~45;
P=20~300, preferably 100~150.
The molar ratio of the acrylamide, N- Benzyl-N-ethyls acrylamide and vinyl acetate is 1: 0.5~3:
0.1~2.5, preferably 1: 1.5: 2.
Preferably, the degreaser molecular weight is 20000~30000.
It is a further object to provide a kind of preparation method of heavy crude heat extraction sewage degreaser, the preparation sides
Method includes the following steps:
(1) the N- benzyl-N- second of deionized water and aforementioned proportion is added in the three-necked flask equipped with thermometer, stirring rod
Base acrylamide is warming up to 30~40 DEG C, 20~30min of constant temperature under 200~300rpm stir speed (S.S.)s;
(2) acrylamide of aforementioned proportion is added in above-mentioned three-necked flask, and temperature is risen to 45~50 DEG C, be added
Hydrophobic grouping solubilizer stirs 30~40min, and stir speed (S.S.) is 500~550rpm, and after mixing time, temperature rises to 60
~65 DEG C, 20~30min of constant temperature obtains mixture;
(3) it uses the sodium hydroxide solution of 6mol/L to adjust the pH value of mixture, makes pH value between 7~8, by aforementioned proportion
Vinyl acetate be added to adjustment pH value after mixture in, adjustings stir speed (S.S.) be 300~400rpm, thermostat temperature 40~
50 DEG C, after stirring 10~30min, initiator is added, temperature rises to 70~85 DEG C, and stir speed (S.S.) is 400~500rpm, and constant temperature is anti-
2~6h is answered, stirring is stopped, Temperature fall obtains polymer solution;
(4) polymer solution is transferred in round-bottomed flask, is evaporated under reduced pressure, obtains gum-like product, 3~5 are washed with acetone
It is secondary, it is then placed in drying box dry 12~for 24 hours, finally obtain acrylamide/N- Benzyl-N-ethyls acrylamide/acetic acid second
Enester polymer.
The dosage of the deionized water is 5~15 times of acrylamide monomer quality;The hydrophobic grouping solubilizer
For lauryl sodium sulfate or dodecyl sodium sulfate, dosage is the 0.5~2.0% of acrylamide monomer quality;Described draws
Hair agent is K2S2O8Or NaHSO3, dosage is the 2.5~5.0% of acrylamide monomer quality.
The reaction equation is as follows:
The present invention is provided to the degreasers of oil-field thick-oil thermal recovery sewage disposal, belong to amphipathic polymer molecule, this is poly-
Contain ester group, amide groups, phenyl ring and tertiary amine group on adduct molecule, the hydrophobic chain in amphipathic polymer molecule is with block
Formal distribution, can be adsorbed with the oil in sewage, and the polar group on side chain is then easy to be deep into greasy dirt, be easy to it is thick
Complexing occurs for the gum asphalt in oil, promotes the flocculation of greasy dirt, and then achieve the purpose that condensed oil sewage oil removal treatment.
In addition, the present invention introduces vinyl acetate when designing oil removing agent molecule, which has flexibility and elasticity, and permeates
Performance is good, stronger for the covering property of thicker crude oil;The group introduced in this molecule simultaneously belongs to nonionic, has
Stronger salt-tolerant trait and heat-resisting property.
The present invention has the following advantages that compared with prior art and advantageous effect:
(1) raw material sources of degreaser of the invention are extensive, and synthesis technology is simple, and product is easily obtained and transports preservation;
(2) degreaser of the invention is adaptable, and dosage is few, can meet the needs of environmental protection and oil field development;
(3) degreaser of the invention has temperature resistance salt resistant character, can heatproof reach 210000mg/ up to 220 DEG C, resistance to salinity
L;
(4) degreaser of the invention has the characteristics that oil removal efficiency is high to heavy crude heat extraction sewage processing, heavy crude heat extraction sewage
Oil removal rate up to 96% or more, more existing medicament improves 45% or more, meets the pretreated requirement of oil removing of condensed oil sewage;
(5) degreaser of the invention is environmentally safe, and oil removing can be recycled.
Specific implementation mode
The present invention is described in further detail with reference to specific embodiment, and with reference to data.It should be understood that these embodiments
It is of the invention solely for the purpose of illustration, rather than limit the scope of the invention in any way.
Embodiment 1:Degreaser A1And preparation method thereof
(1) degreaser A1Composition, component and molecular weight it is as follows:
Degreaser A1By acrylamide, N- Benzyl-N-ethyls acrylamide and vinyl acetate according to 1: 0.5: 0.1 mole
It is made than passing through micellar free radical copolymerization method, average molecular weight 8000.
(2) degreaser A1Preparation method it is as follows:
1. the N- benzyls-of 355.4g deionized waters and 0.5mol are added in the three-necked flask equipped with thermometer, stirring rod
N- ethyl acrylamides are warming up to 30 DEG C, constant temperature 20min under 200rpm stir speed (S.S.)s;
2. the acrylamide of 1mol is added in above-mentioned three-necked flask, and temperature is risen to 45 DEG C, 0.36g 12 is added
Sodium alkyl sulfate stirs 36min, stir speed (S.S.) 500rpm, and after mixing time, temperature rises to 60 DEG C, and constant temperature 25min is obtained
To mixture;
3. adjusting the pH value of mixture with the sodium hydroxide solution of 6mol/L, make pH value 7, by the vinyl acetate of 0.1mol
Ester is added in the mixture after adjusting pH value, and adjusting stir speed (S.S.) is 300rpm, and 40 DEG C of thermostat temperature adds after stirring 20min
Enter 1.78g K2S2O8, temperature rises to 70 DEG C, stir speed (S.S.) 400rpm, isothermal reaction 2h, stops stirring, and Temperature fall obtains
Polymer solution;
4. polymer solution is transferred in round-bottomed flask, it is evaporated under reduced pressure, obtains gum-like product, washs 3 times with acetone, so
After be put into drying box dry 12h, finally obtain acrylamide/N- Benzyl-N-ethyls acrylamide/vinyl acetate polymer
A1。
Embodiment 2:Degreaser A2And preparation method thereof
(1) degreaser A2Composition, component and molecular weight it is as follows:
Degreaser A2By acrylamide, N- Benzyl-N-ethyls acrylamide and vinyl acetate according to 1: 1.5: 2 molar ratio
It is made by micellar free radical copolymerization method, average molecular weight 25000.
(2) degreaser A2Preparation method it is as follows:
1. the N- benzyls-of 710.8g deionized waters and 1.5mol are added in the three-necked flask equipped with thermometer, stirring rod
N- ethyl acrylamides are warming up to 35 DEG C, constant temperature 25min under 260rpm stir speed (S.S.)s;
2. the acrylamide of 1mol is added in above-mentioned three-necked flask, and temperature is risen to 48 DEG C, 0.71g 12 is added
Sodium alkyl sulfonate stirs 30min, stir speed (S.S.) 520rpm, and after mixing time, temperature rises to 63 DEG C, and constant temperature 20min is obtained
To mixture;
3. adjusting the pH value of mixture with the sodium hydroxide solution of 6mol/L, make pH value 7.5, by the vinyl acetate of 2mol
Ester is added in the mixture after adjusting pH value, and adjusting stir speed (S.S.) is 360rpm, and 45 DEG C of thermostat temperature adds after stirring 10min
Enter 2.84g NaHSO3, temperature rises to 80 DEG C, stir speed (S.S.) 460rpm, isothermal reaction 4h, stops stirring, and Temperature fall obtains
Polymer solution;
4. polymer solution is transferred in round-bottomed flask, it is evaporated under reduced pressure, obtains gum-like product, washs 4 times with acetone, so
After be put into drying box dry 18h, finally obtain acrylamide/N- Benzyl-N-ethyls acrylamide/vinyl acetate polymer
A2。
Embodiment 3:Degreaser A3And preparation method thereof
(1) degreaser A3Composition, component and molecular weight it is as follows:
Degreaser A3By acrylamide, N- Benzyl-N-ethyls acrylamide and vinyl acetate according to 1: 3: 2.5 molar ratio
It is made by micellar free radical copolymerization method, average molecular weight 48000.
(2) degreaser A3Preparation method it is as follows:
1. the N- benzyls-N- of 1066.2g deionized waters and 3mol is added in the three-necked flask equipped with thermometer, stirring rod
Ethyl acrylamide is warming up to 40 DEG C, constant temperature 30min under 300rpm stir speed (S.S.)s;
2. the acrylamide of 1mol is added in above-mentioned three-necked flask, and temperature is risen to 50 DEG C, 1.42g 12 is added
Sodium alkyl sulfonate stirs 40min, stir speed (S.S.) 550rpm, and after mixing time, temperature rises to 65 DEG C, and constant temperature 30min is obtained
To mixture;
3. adjusting the pH value of mixture with the sodium hydroxide solution of 6mol/L, make pH value 8, by the vinyl acetate of 2.5mol
Ester is added in the mixture after adjusting pH value, and adjusting stir speed (S.S.) is 400rpm, and 50 DEG C of thermostat temperature adds after stirring 30min
Enter 3.55g NaHSO3, temperature rises to 85 DEG C, stir speed (S.S.) 500rpm, isothermal reaction 6h, stops stirring, and Temperature fall obtains
Polymer solution;
4. polymer solution is transferred in round-bottomed flask, it is evaporated under reduced pressure, obtains gum-like product, washs 5 times with acetone, so
After be put into drying box it is dry for 24 hours, finally obtain acrylamide/N- Benzyl-N-ethyls acrylamide/vinyl acetate polymer
A3。
4 degreaser A of embodiment1Field application
Multi-purpose station F8Water be heavy crude heat extraction sewage, test process scale be 80m3/ d, water oil content 425mg/L, it is dirty
Water salinity 9856mg/L utilizes the degreaser A of the present invention1To multi-purpose station F8Sewage carry out oil removal treatment, after adding degreaser
A concentration of 45mg/L of degreaser in sewage, oil content is reduced to 10.2mg/L after processing, and oil content reduces by 97.6%, reaches work
Skill requirement.
4 degreaser A of embodiment2Field application
Multi-purpose station F3Water be heavy crude heat extraction sewage, test process scale be 50m3/ d, water oil content 726mg/L, it is dirty
Water salinity 15683mg/L utilizes the degreaser A of the present invention2To multi-purpose station F3Sewage carry out oil removal treatment, add degreaser
Afterwards in sewage degreaser a concentration of 65mg/L, oil content is reduced to 10.9mg/L after processing, and oil content reduces by 98.5%, reaches
Technological requirement.
6 degreaser A of embodiment3Field application
Multi-purpose station F12Water be heavy crude heat extraction sewage, test process scale be 60m3/ d, water oil content 368mg/L,
Sewage salinity 7853mg/L utilizes the degreaser A of the present invention3To multi-purpose station F12Sewage carry out oil removal treatment, add oil removing
After agent in sewage degreaser a concentration of 32mg/L, oil content is reduced to 11.0mg/L after processing, and oil content reduces by 97.0%, reaches
To technological requirement.