CN1138706C - Compound oil-bearing effluent flucculant - Google Patents
Compound oil-bearing effluent flucculant Download PDFInfo
- Publication number
- CN1138706C CN1138706C CNB001107054A CN00110705A CN1138706C CN 1138706 C CN1138706 C CN 1138706C CN B001107054 A CNB001107054 A CN B001107054A CN 00110705 A CN00110705 A CN 00110705A CN 1138706 C CN1138706 C CN 1138706C
- Authority
- CN
- China
- Prior art keywords
- component
- flocculation agent
- add
- amine
- functional groups
- 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.)
- Expired - Lifetime
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention provides a compound flocculant for treating oily waste water, which comprises component A and component B, wherein the component A is obtained by compounding of an amine linear low molecular weight polymer with a plurality of hydroxyl radical functional groups and PAC; the component B is a dithiocarbamate flocculant. Both of the component A and the component B can be singly used as a demulsifying flocculant. When the demulsifying flocculant of the present invention is used for treating oily waste water of oil refinery or an oil field, the operation of demulsification and flcculation for oil removal can be completed simultaneously, and the amount of generated floating dregs is greatly reduced as compared with that of the existing preparation.
Description
Technical field
The present invention relates to a kind of compound oil-bearing effluent flucculant and preparation process thereof, especially for the flocculation agent and the preparation process thereof of the oily(waste)water of handling the generation of oil field and petroleum refining process.
Background technology
In refining of petroleum and oil production process, produce a large amount of oily(waste)waters, except that containing crude oil Semi-polarity compound, also bring a large amount of tensio-active agents into, increased the weight of the pollution level of oily(waste)water.
The oily(waste)water that oil field or refinery produce enters pipe network usually and converges and focus on to the sewage-farm, and treatment facility generally has oil trap, flotation cell and biochemical reactor etc.After removing oil slick, thick dispersed oil in advance, enter the flotation facility, in such waste-oil scavenger, to add flocculation agent usually to remove the middle remaining oil that anhydrates, water is further purified.
The most frequently used flocculation agent is inorganic polymeric aluminum (abbreviating PAC as), and its breaking milk and removing oil is functional, low price, and the treat effluent transparency is good.But maximum shortcoming is that the scum silica frost amount that produces is big, the water content of slag up to 95%-99% about, and loose, the easy fragmentation of flco.Bring very big difficulty for the scum silica frost aftertreatment.
Chinese patent CN 85107131 has introduced the flocculation agent that is used to handle oily(waste)water based on inorganic aluminate, molysite, when using this agent to dispose of sewage, produces scum silica frost a large amount of, that water ratio is very high, brings secondary pollution.
What Chinese patent CN 90106284 proposed handles oily(waste)water with dimethyl-dipropenyl ammonium chloride and acrylamide copolymer, it is few to produce the quantity of slag when using this class flocculation agent to handle oily(waste)water, but breakdown of emulsion is poor, just can not satisfy actual needs when handling emulsified oily watewater.
A kind of composite flocculant that Chinese patent CN 89107966 proposes is by industrial aluminum sulphate, industrial calcium chloride, calcium hydroxide, powdered activated carbon and five kinds of composite forming of raw material of polyacrylamide.It is said that this composite flocculation agent has functions such as flocculation, absorption and bridge formation, deoiling effect is preferably arranged when handling petrochemical effluent.But this flocculation agent needs to add 200-300mg/l in use, and so big dosage not only makes production cost increase, and produces too much scum silica frost.In addition a large amount of soluble inorganic salts is introduced water body, also cause secondary pollution, bring difficulty for the reuse of purifying waste water.
The dithiocarbamate(s) water purification agent makes with substance reactions such as certain polyamine species, epoxy compounds, organic pure and mild dithiocarbonic anhydride, this flocculation agent uses when handling oily(waste)water at first, the scum silica frost that produces becomes thick, mobile poor, attached to the limit wall of treatment facility or scrape on the slag equipment, force the entire treatment process shutdown to be cleared up.U.S. Pat 4855060 and US5006274 flco too multiviscosisty call uncontrollable problem.
Summary of the invention
The object of the present invention is to provide and a kind ofly produce mud and scum silica frost is few, the toughness of scum silica frost is low, the flocculation agent consumption is little, produce that slag is few, demulsification performance is strong, oil removal efficiency is high, effluent quality is good, the composite flocculant that is used for oil field and refinery's oily water treatment and the preparation and the using method of wide adaptability.
Composite flocculant of the present invention is made up of component A and B component.Component A is compound by linear low-molecular weight polymer W of the amine that has a plurality of hydroxy functional groups and inorganic flocculating agent, and W and inorganic flocculating agent compositely proportional are 1: 0.1～1: 10 by weight, are preferably 1: 0.5～1: 5.The linear low-molecular weight polymer W of amine that has a plurality of hydroxy functional groups can have following structure:
Wherein n is the integer of 2-6, and m is the integer of 10-30.B component is the dithiocarbamate(s) flocculation agent, and its typical structure is:
R in the formula " is-R-NH
2Or
Structure,
R is linear pattern, ramiform or ring texture alkylidene group; Arylidene; Straight chain, side chain or ring texture substituted alkylene; Replace arylidene or its mixture;
R ' is-[CH
2-]
m-O-R-O-[-CH
2-]
m-
N and m are respectively the integer of 1-5, and q is 0 or 1; X is hydrogen, basic metal or ammonium ion.
The ratio of the compound use of A and B is by weight: 1: 0.01～1: 1, be preferably 1: 0.05～1: 0.5.
W among the component A is for obtaining an intermediate product by polyamines type organic and the reaction of simple function group oxygen-bearing organic matter, the reddish-brown transparent liquid that this intermediate product gets with the reaction of bifunctional chlorinated organics again, its building-up process has comparatively detailed description in USP4029708, its building-up process is: add the polyamines type organic in reactor, as triethylenetetramine, diethylenetriamine, hexamethylenediamine, in the ethylene triamine etc. one or more, add the simple function group oxygen-bearing organic matter when being heated to 20～60 ℃, as propylene oxide and/or oxyethane etc., 1-24 hour 30-150 ℃ of following reaction times of condition, obtain a kind of linear low-molecular weight polymer of amine that has a plurality of hydroxy functional groups.Form intermediate product and replace amine.Add bifunctional chlorinated organics such as Epicholorohydrin and/or Ethylene Dichloride etc. again, add termination reactions such as mineral acid, example hydrochloric acid and/or sulfuric acid at last, get the transparent sticky polymers W of reddish-brown.
Inorganic flocculating agent among the component A is selected from one or more in poly aluminium chloride (PAC), ferrous sulfate, the Tai-Ace S 150 etc.Above-mentioned polymkeric substance that obtains and inorganic flocculating agent is composite as finishing in reactor according to a certain percentage.Earlier PAC is dissolved in a certain amount of water.Add W then, the two part by weight is 1: 0.1～10, better is 1: 0.5～5.Stir, form flowable thick liquid, be called component A.
B component is the dithiocarbamate(s) flocculation agent, and its building-up reactions has comparatively detailed description at USP5247087.It is by polyamines and insatiable hunger resin (as Resins, epoxy) reaction, and the intermediate of generation reacts under alkaline medium with dithiocarbonic anhydride and generates the dithiocarbamate(s) polymkeric substance, and reaction process is finished in pure medium usually.
Component A and B component mixed in proportion both obtain composite flocculant of the present invention.
Flocculation agent of the present invention adds in the handled sewage after according to the measure of precision of using appts flocculation agent being diluted to finite concentration in use.
Advantage of the present invention is that employing differs from one another, oily(waste)water is handled in the compound use of three kinds of flocculation agents of performance complement, plays the effect of breakdown of emulsion, flocculation, bridge formation simultaneously.Flocculant component A and B component can be used for handling oily(waste)water separately.Component A shows good demulsification performance and deoiling effect when handling oily(waste)water.But the flco of its formation is tiny, and is slower with water sepn speed, and formed scum silica frost is loose and be easy to fragmentation.After adding flocculant component B, to having tangible cohesion bridging action by the formed tiny flco of A flocculation agent, add a spot of B component after, not only obviously reduce the add-on of A component when disposing of sewage, and the tiny flco behind the breakdown of emulsion wads a quilt with cotton into bulk at once, separates rapidly with water.Be more significantly, formed scum silica frost oleaginousness height behind the adding polymeric flocculant, water ratio is low, and the scum silica frost amount reduces 30w%-50w% than PAC flocculation agent.This multicomponent polymeric has multiple functional groups such as hydroxyl, amido in addition, the electric density height, and breakdown of emulsion is strong, good water solubility.
Embodiment
Following example is used for further specifying the advantage of flocculation agent of the present invention.
Embodiment 1
The preparation of polymkeric substance W: at a volume that has stirring system, thermometer, condensing reflux is in the there-necked flask of 1L, add the quadrol of 60 grams and the propylene oxide of 116 grams, temperature is controlled at 60 ℃, and reaction is carried out promptly getting in 2.5 hours intermediate product and replaced amine, and this product is a colourless transparent liquid, add 92.5 gram epoxy chloropropane then, temperature is 70 ℃, after reaction is carried out 5 hours, can make it be cooled to room temperature, and then adding 120 gram hydrochloric acid, products therefrom is for combining look dope W.
The preparation of component A: the polymkeric substance W and the ferrous sulfate of above-mentioned preparation is composite by 1: 0.7 weight ratio at normal temperatures, obtain component A.
The preparation of B component: in a there-necked flask that has stirring system, thermometer and a prolong, add quadrol 13 grams, propylene glycol 30 grams, Resins, epoxy 47 grams, 60 ℃ of reactions 3 hours, add 45% potassium hydroxide aqueous solution, 50 grams, drip dithiocarbonic anhydride 21 grams simultaneously, continue reaction 1 hour under 30 ℃ of conditions, products therefrom is a B component.
Component A and B are by composition of proportions in 1: 1 flocculation agent 1 of the present invention.
Embodiment 2
The preparation of component W: in a there-necked flask that has stirring system, thermometer and a prolong, add triethylenetetramine 73.12 grams, add simple function group compound oxyethane 88 grams, temperature maintenance is at 120 ℃, reaction was carried out 12 hours, add bifunctional Ethylene Dichloride 40 grams then, temperature of reaction was carried out under 150 ℃ 18 hours, added technical hydrochloric acid 67 grams at last, obtained polymkeric substance W.
The preparation of component A: first water is dissolved in the water PAC fully, adds above-mentioned polymkeric substance W then, and the two weight ratio is 1: 1, stirs homogeneous and obtains component A.
The preparation of B component: as the preparation method of B component in the example 1, add 26 gram quadrols, propylene glycol 122 grams, Resins, epoxy 100 gram, 65 ℃ of reactions 5 hours, temperature of reaction is reduced to room temperature after, add 45% potassium hydroxide aqueous solution, 80 grams and 40 gram water, drip dithiocarbonic anhydride 50 grams simultaneously, be warmed up to after reaction finishes and continue reaction 1 hour under 35 ℃ of conditions, products therefrom is flocculation agent component B.
Component A and B are by composition of proportions in 1: 0.5 flocculation agent 2 of the present invention.
Embodiment 3
The preparation of component W: with a volume is that three mouthfuls of reaction flasks of 1000ml place water-bath, add the hexanediamines of 116 grams and make warming-in-water to 40 ℃, add 116 gram propylene oxide again, temperature is controlled at 80 ℃ and keeps reaction in 7 hours, obtain replacing amine, at epoxy chloropropane 73.9 grams that add bifunctional, make temperature of reaction be controlled at 110 ℃ and continue 10 hours then, add 120 gram hydrochloric acid at last, and make its cool to room temperature promptly get component W.
The preparation of component A: above-mentioned polymkeric substance W and inorganic flocculating agent poly aluminium chloride (PAC) is composite, and method is with embodiment 2, and the two weight ratio is 1: 4.Stir homogeneous, form flowable thick liquid, obtain component A.
The preparation of B component: with the preparation of B component among the embodiment 1.
Component A and B are by composition of proportions in 1: 0.5 flocculation agent 3 of the present invention.
Embodiment 4
The preparation of component W: the method identical with example 3 produced component W.
The preparation of component A: above-mentioned polymkeric substance W and inorganic flocculating agent poly aluminium chloride (PAC) is composite, and method is with embodiment 2, and the two weight ratio is 1: 1.Stir homogeneous, form flowable thick liquid, obtain component A.
The preparation of B component: with the preparation of B component among the embodiment 1.
Component A and B are by composition of proportions in 1: 0.5 flocculation agent 4 of the present invention.
Embodiment 5
The preparation of component W: the method identical with example 3 produced component W,
The preparation of component A: above-mentioned polymkeric substance W and inorganic flocculating agent poly aluminium chloride (PAC) is composite, and method is with embodiment 2, and the two weight ratio is 1: 1.Stir homogeneous, form flowable thick liquid, obtain component A.
The preparation of B component: with the preparation of B component among the embodiment 1.
Component A and B join pending oily(waste)water respectively by composition of proportions in 1: 0.3 flocculation agent 5 of the present invention, and sewage is purified.
Embodiment 6
Adopt flocculation agent 1-3 to handle certain oil field waste, and compare with poly aluminium chloride (PAC)., during use each flocculation agent being diluted to 1w%, its test-results is listed in table 1.
Table 1 example product flocculation agent is to the treatment effect of certain oil-contaminated water of oil field
| The flocculation agent title | Dosage Mg/l | Oil-contg mg/l | Oil removal rate % | Remarks | |
| Former water | Water outlet | ||||
| Flocculation agent 1 | 10 | 680 | 82.9 | 87.8 | Breakdown of emulsion, water colour clarification |
| Flocculation agent 2 | 10 | 680 | 41.2 | 93.9 | The same |
| Flocculation agent 3 | 5 | 680 | 62.0 | 90.9 | The same |
| Flocculation agent 3 | 10 | 680 | 40.0 | 94.1 | The same |
| Flocculation agent 3 | 20 | 680 | 26.8 | 96.1 | The same |
| PAC | 10.0 | 680 | - | Breakdown of emulsion not | |
| PAC | 30.0 | 680 | - | Breakdown of emulsion not | |
| PAC | 50.0 | 680 | 430 | 36.8 | Slight breakdown of emulsion |
| PAC | 100.0 | 680 | 131 | 80.7 | Basic breakdown of emulsion |
Good effect of demulsification and oil removal is just arranged when as seen example 1-3 flocculation agent all has remarkable demulsification, particularly flocculation agent 3 dosages low to oil-contaminated water of oil field.And when adopting the PAC flocculation agent to handle this water, dosage has only slight breakdown of emulsion at 50mg/l, when dosage increases to 100mg/l, just reaches basic breakdown of emulsion, and irreducible oil content is still greater than 100mg/l in the water outlet.Show that flocculation agent 1-3 has excellent treatment effect to oil field waste.
Embodiment 7
Oil-contaminated water of oil field is contained in the beaker of 1000ml, adds the flocculation agent of three kinds of different varietiess simultaneously, under 200 rev/mins of conditions, stirred 3 minutes fast, under 80 rev/mins condition, stirred at a slow speed 2 minutes, static 30 minutes, get supernatant liquor and analyze oily oil-containing, measure the scum silica frost amount that produces simultaneously.The results are shown in Table 2.
Table 2 is handled the oil and the slag analytical results of Liaohe Oil Field oily(waste)water with composite flocculation agent of the present invention
| Flocculation agent | Dosage mg/l | The oily mg/l of intaking | Water outlet oil mg/l | Produce quantity of slag ml/100ml | Slag reduction % | The flowability of slag |
| PAC | 550 | 1670 | 63.8 | 25 | Benchmark | Fine |
| Embodiment 4 | 550 | 1670 | 63.0 | 15 | 40 | Fine |
| Embodiment 5 | 550 | 1670 | 36.5 | 10 | 60 | Fine |
This shows that the deoiling effect of flocculation agent of the present invention and the product quantity of slag all are best, the flocculation agent that the present invention forms can also be handled petrochemical enterprise oily(waste)water and grease factory oily(waste)water, chemical plant oily(waste)water etc. except being used to handle the oil field waste.
Claims (7)
1, a kind of composite flocculant, form by component A and B component, wherein component A is compound by linear low-molecular weight polymer of the amine that has a plurality of hydroxy functional groups and inorganic flocculating agent, the linear low-molecular weight polymer of amine and the inorganic flocculating agent compositely proportional that have a plurality of hydroxy functional groups by weight are 1: 0.1～1: 10, B component is a dithiocar-bamate, and the ratio of the compound use of A and B is 1: 0.01～1: 1 by weight; The described linear low-molecular weight polymer of amine that has a plurality of hydroxy functional groups has following structure:
Wherein n is the integer of 2-6, and m is the integer of 10-30; Described dithiocar-bamate B has following structure:
R in the formula " is-R-NH
2Or
Structure,
R is linear pattern, ramiform or ring texture alkylidene group; Arylidene; Straight chain, side chain or ring texture substituted alkylene; Replace arylidene or its mixture;
R ' is-[CH
2-]
m-O-R-O-[-CH
2-]
m-
N and m are respectively the integer of 1-5, and q is 0 or 1; X is hydrogen, basic metal or ammonium ion.
2,, it is characterized in that described linear low-molecular weight polymer of amine and the inorganic flocculating agent compositely proportional that has a plurality of hydroxy functional groups by weight is 1: 0.5～1: 5 according to the described flocculation agent of claim 1.
3,, it is characterized in that the compound ratio of described A and B is by weight: 1: 0.05～1: 0.5 according to the described flocculation agent of claim 1.
4,, it is characterized in that described inorganic flocculating agent is selected from one or more in poly aluminium chloride, ferrous sulfate, the Tai-Ace S 150 according to the described flocculation agent of claim 1.
5, according to the described flocculation agent of claim 1, it is characterized in that the described linear low-molecular weight polymer of amine that has a plurality of hydroxy functional groups adopts following process preparation: in reactor, add the polyamines type organic, add the simple function group oxygen-bearing organic matter when being heated to 20～60 ℃, 1-24 hour 30-150 ℃ of following reaction times of condition, add the bifunctional chlorinated organics then, add the mineral acid termination reaction at last.
6,, it is characterized in that described polyamines type organic is selected from one or more in triethylenetetramine, diethylenetriamine, hexamethylenediamine, the ethylene triamine according to the described flocculation agent of claim 5; Described simple function group oxygen-bearing organic matter is selected from propylene oxide and/or oxyethane; Described bifunctional chlorinated organics is selected from Epicholorohydrin and/or Ethylene Dichloride; Described mineral acid is selected from hydrochloric acid and/or sulfuric acid.
7, according to the described flocculation agent of claim 1, it is characterized in that described dithiocar-bamate by polyamines and the reaction of insatiable hunger resin, the intermediate of generation reacts under alkaline medium with dithiocarbonic anhydride and generates the dithiocarbamate(s) polymkeric substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001107054A CN1138706C (en) | 2000-07-24 | 2000-07-24 | Compound oil-bearing effluent flucculant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001107054A CN1138706C (en) | 2000-07-24 | 2000-07-24 | Compound oil-bearing effluent flucculant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1335269A CN1335269A (en) | 2002-02-13 |
| CN1138706C true CN1138706C (en) | 2004-02-18 |
Family
ID=4580684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001107054A Expired - Lifetime CN1138706C (en) | 2000-07-24 | 2000-07-24 | Compound oil-bearing effluent flucculant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1138706C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757885B (en) * | 2008-12-25 | 2012-07-25 | 恩达电路(深圳)有限公司 | Heavy metal chelating agent and preparation method thereof |
| CN101935096A (en) * | 2010-08-17 | 2011-01-05 | 海安县中丽化工材料有限公司 | Production method of decolorizing flocculant capable of reducing COD |
| GB201511376D0 (en) * | 2015-06-29 | 2015-08-12 | Ecolab Usa Inc | Process for the treatment of produced water from chemical enhanced oil recovery |
| CN106335969B (en) * | 2016-10-19 | 2020-09-08 | 中国石油化工股份有限公司 | High-polymer-content heavy oil sewage treating agent |
| CN113413643B (en) * | 2021-07-26 | 2022-07-01 | 中建西部建设建材科学研究院有限公司 | Efficient settling method for waste slurry of concrete mixing plant |
-
2000
- 2000-07-24 CN CNB001107054A patent/CN1138706C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1335269A (en) | 2002-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1170778C (en) | Rapid coagulation-flocculation and sedimentation type waste water treatment method | |
| CN100334013C (en) | Thick oil, super thick oil effluent purifier | |
| CN103708631B (en) | A kind of multi-function sewage treating agent and preparation method thereof | |
| CN101041495A (en) | High polymer composite coagulant for treatment of oily waste water and making method thereof | |
| CN101050381A (en) | Deemulsifier for lowering oil content in drainage of electrical desalting /dewatering, and preparation method | |
| CN1955122A (en) | Method for treating oil-containing waste water | |
| CN1137857C (en) | Oily sewage processing method | |
| CN1724404A (en) | Flocculation agent of poly ferric-dimethyl diallyl ammonium chloride homopolymer inorganic organic composited and preparation process thereof | |
| CN1138011A (en) | Improved process for removing phosphate | |
| CN1138706C (en) | Compound oil-bearing effluent flucculant | |
| CN113582316A (en) | Dithiocarbamate water purifier and preparation method and application thereof | |
| KR100413203B1 (en) | No wasting activated sludge process | |
| CN1821114A (en) | Process for preparing composite floculating agent of aluminium sulfate and slaked lime | |
| CN1817803A (en) | Safety and ecological natural built-up flocculant, its production and use | |
| US6126837A (en) | Method for removing suspended particles using mannich-derived polyethers | |
| CN101746868A (en) | Composite flocculant for treating oily wastewater | |
| CN106396066A (en) | Water purifying agent for treatment process of polymer-containing sewage pipeline of offshore oil field and application of water purifying agent | |
| CN1110455C (en) | Compound demulsifying flocculant | |
| CN100340506C (en) | Sludge dewatering agent and its preparation method | |
| CN1233567C (en) | Organic polymer flocculating agent and preparing process thereof | |
| CN1088043C (en) | Demulsification type organic flocculant and preparation process thereof | |
| CN1144762C (en) | Process for treating recovering water of crude oil | |
| CN1055451C (en) | Cation coagulant | |
| CN1254526C (en) | Preparation method of cooling lubricating liquid for stone processing | |
| Rizayev et al. | TREATMENT OF OILY WASTEWATER |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040218 |
|
| CX01 | Expiry of patent term |