CN1911828A - Modified lignin oil removing flocculant and its preparation method - Google Patents
Modified lignin oil removing flocculant and its preparation method Download PDFInfo
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Abstract
The present invention discloses one kind of modified lignin deoiling flocculant and its preparation process. The preparation process includes the following steps: mixing lignin and water in the reactor through stirring, regulating the reaction system pH value to 9.5-11.5, heating to 65-95 deg.c, adding aldehyde compound to react for 10-30 min, adding nitrogen compound, further reaction for 2.0-4.0 hr, cooling to 0-25 deg.c, adding alkali solution while dropping CS2, reacting for 2.0-5.0 hr, heating to 50-75 deg.c, further reacting for 1.0-4.0 hr, cooling and discharging. The deoiling flocculant of modified lignin has molecular weight 5000-50000, contains dithiocarbamate radical, and has high performance/cost ratio. The preparation process is one environment friendly clean process.
Description
Technical field:
The invention belongs to field of fine chemical, specially refer to a kind of modified lignin oil removing flocculant of handling oily(waste)water and preparation method thereof that is used to.
Background technology:
The world today, the deposit of oil, natural gas source is limited, and their research, development and utilization is on the rise to the influence that ball ecological environment brings, and this has impelled is that the macromolecular material of raw material is greatly developed with natural resource.Xylogen is very big in the quantity that occurring in nature exists, and always with the Mierocrystalline cellulose association, whole world terrestrial plant can produce 50,000,000,000 tons of xylogen every year, wherein the industrial lignin that produces in the cooking waste liquor of pulp and paper industry has 3,000 ten thousand tons.The history in existing several thousand of human use's Mierocrystalline cellulose, the xylogen that really begins one's study then has been the thing after nineteen thirty, and xylogen is not also well utilized so far, the xylogen of China only about 6% obtains utilizing.Xylogen owing to be not fully utilized, has become one of primary pollution source in the paper industry as the by product of wood saccharification industry and paper industry, and this not only causes serious environmental to pollute, and causes the significant waste of resource.The comprehensive utilization of the so-called xylogen in some paper mill also just is concentrated to finite concentration with sulfite waste lye, or with the sulfonation of alkaline cooking black liquor be concentrated to finite concentration, the user is given in dispersion agent and binding agent direct marketing as low grade, and added value is not high, and the enthusiasm of enterprise is not high yet.Therefore, how effectively to make good use of this renewable resources of xylogen, improve its added value, and the solution problem of environmental pollution becomes starting point of the present invention.
At present, the processing of oily(waste)water and qualified discharge have become the important topic of current environmental protection.Especially for some oily(waste)water,,, utilize the water quality of the water after the prior art processing not reach water filling and sewage discharge requirement along with producing and the further raising of environmental requirement as oil field extracted water etc.Therefore, when transforming existing installation or developing novel water treating equipment, the inexorable trend that efficient, the wide sewage-treating agent of imitating of research and development is present sewage disposal technology development.The external novel de-oiling agent dithiocar-bamate (Dithiocarbamate is called for short DTC) of mainly utilizing U.S.'s exploitation eighties in 20th century, and auxiliary other chemical agent is handled oily(waste)water.And China only is in preliminary development to the research of this class chemical agent, does not form industrialization as yet, and major cause has following two aspects: one, China is later to the research starting point of dithiocar-bamate; Two, the preparation raw material of dithiocar-bamate is with CS
2And organic amine (dimethylamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA) or polyamines polyene etc.) is main, the prices of raw and semifnished materials are higher, and then influence the price of dithiocar-bamate product, thereby be unfavorable for that product applies in oily(waste)water is handled.
Therefore, if with the xylogen is raw material, develop the modified lignin oil removing flocculant that contains the dithiocar-bamate group by chemical modification, then not only reduce the price of dithiocar-bamate product greatly, help applying of modified lignin oil removing flocculant, and will further widen the range of application of xylogen, and improve its added value, also improve simultaneously enterprise's comprehensive utilization xylogen and solve the enthusiasm that pulping back liquor pollutes, promote China's pulping and paper-making industry to continue, develop in a healthy way.
Summary of the invention:
The objective of the invention is to overcome the deficiencies in the prior art, improve the added value of xylogen and solve problem such as dithiocar-bamate degreaser cost height, a kind of modified lignin oil removing flocculant and preparation method thereof is provided.Promptly utilizing the by product-xylogen in the pulp industry is raw material, adopt totally enclosed feed way and to bathe to synthesize and prepare modified lignin oil removing flocculant, to reduce or eliminate in production and the use to the environment produced pollution, on the basis that reduces product cost greatly, the present invention improves the oil removing and the flocculation synergy performance of product, so that can apply in engineering.
A kind of modified lignin oil removing flocculant provided by the present invention and preparation method thereof, it is characterized in that described modified lignin oil removing flocculant contains the dithiocar-bamate group, the content of dithiocar-bamate group is 2.0～6.7mmol in every gram modified lignin oil removing flocculant, the modified lignin oil removing flocculant relative molecular mass is 5000～50000, be chocolate thick liquid or chocolate brown powder, the solubleness of chocolate brown powder in the time of 28.0 ℃ is 35.0～45.0g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 9.0～10.5, the solution density of massfraction 40% is 1.16～1.25g/L, the chemical stability height.
The concrete technology of above-mentioned modified lignin oil removing flocculant is as follows:
1. raw material and prescription (massfraction):
Xylogen: 2.5～20.0%
Aldehyde compound: 2.0～25.0%
Nitrogenous compound: 8.0～25.0%
Dithiocarbonic anhydride: 10.0～30.0%
Alkali lye: 3.0～40.0%
Water: 10.0～50.0%
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier xylogen and water are added in the reactor, after stirring, the pH value of reaction system is transferred to 9.5～11.5, add aldehyde compound behind heat temperature raising to 65～95 ℃, add nitrogenous compound behind reaction 10～30min, continue to be cooled to 0～25 ℃ behind reaction 2.0～5.0h, drip dithiocarbonic anhydride when slowly adding alkali lye then, behind reaction 2.0～5.0h, be warming up to 50～75 ℃, continue reaction 1.0～4.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, filter, and get chocolate brown powder with the acetone crystallization.
In this technology, the xylogen that adopts is an alkali lignin, two or more the alkaline process or the kraft process waste liquid of mixed raw material that starting material derive from starting material such as bamboo, bagasse, straw, wheat straw, reed, Eucalyptus, birch, Pinus massoniana Lamb and form according to a certain ratio is by precipitation, separate, extract and obtain alkali lignin; Nitrogenous compound is the mixture of one or more (containing two kinds) in urea, quadrol, diethylenetriamine, tetraethylene pentamine, hexamethylenetetramine, the diethylenetriamine; Alkali lye is sodium hydroxide or potassium hydroxide aqueous solution, and the massfraction of alkali lye is 20.0～60.0%; Aldehyde cpd is formaldehyde, trioxymethylene or Paraformaldehyde 96.
More than the raw material of each step and the massfraction summation of prescription be 100%.
The present invention has the following advantages and positively effect:
1. mainly to utilize the by product-xylogen in the pulp industry be raw material in the present invention, and it is low to make that the product of developing has a cost, and has oil removing and flocculation dual-use function concurrently.
2. the present invention adopts a totally enclosed feed way and a bath synthesis method to prepare modified lignin oil removing flocculant, to reduce or eliminate in the production process starting material to the pollution of environment, and whole process of production do not have " three wastes " (waste gas, waste water, waste residue) discharging, thus this preparation technology be one clean, environmentally friendly technology.
3. product treatment oily(waste)water of the present invention is satisfactory for result, and the dosage of medicament is low: oil removal rate can reduce more than 80.0%, reaches as high as 96.5%, and SS reduces more than 87.0; Reach as high as 98.0%; COD
CrReduce more than 65.0%, reach as high as 76.0%; Colourity reduces more than 80.0%, reaches as high as 91.1%.
4, product stability is good, and is nontoxic, uses and is not subjected to season, region limits, is convenient to deposit and transport.
5. production technique is simple, and raw materials for production are easy to get, and is with short production cycle, reaction temperature and, required equipment is a conventional equipment, is convenient to existing chemical plant and practices midwifery.
Embodiment:
Below the present invention is described in detail:
Embodiment 1: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extracting in the alkaline process masson s pine pulp black liquor): 10.0 kilograms
Formaldehyde (massfraction is 37.0%): 15.0 kilograms
Urea: 12.5 kilograms
Dithiocarbonic anhydride: 15.0 kilograms
Sodium hydroxide (massfraction is 50.0%): 19.5 kilograms
Water: 28.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Alkali lignin and water with the aforementioned calculation amount adds in the reactor earlier, after stirring, with 50.0%NaOH solution the pH value of reaction system is transferred to 10.5, add 15.0 kilograms of formaldehyde behind the heat temperature raising to 85 ℃, add 12.5 kilograms of ureas behind the reaction 10min, continue to be cooled to 15 ℃ behind the reaction 3.0h, drip 15.0 kilograms of dithiocarbonic anhydride when slowly adding 19.5 kilograms of 50.0%NaOH solution then, behind the reaction 3.0h, be warming up to 55 ℃, continue reaction 3.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, filter, and get chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 4.5mmol/g in the product of the present invention, and relative molecular mass is 10000～20000, and massfraction is that 1.0% o'clock pH value of solution value is 10.0, and solution density is 1.20g/L.
Embodiment 2: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extracting in the alkaline process masson s pine pulp black liquor): 8.0 kilograms
Formaldehyde (massfraction is 37.0%): 20.0 kilograms
Urea: 15.0 kilograms
Dithiocarbonic anhydride: 16.0 kilograms
Sodium hydroxide (massfraction is 40%): 25.0 kilograms
Water: 16.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 8.0 kilograms of alkali lignins and 16.0 kg water are added in the reactor, after stirring, with 30.0% sodium radio-phosphate,P-32 solution the pH value of reaction system is transferred to 10.0, add 20.0 kilograms of formaldehyde behind the heat temperature raising to 90 ℃, add 15.0 kilograms of ureas behind the reaction 20min, continue to be cooled to 20 ℃ after the reaction 2.0, drip 16.0 kilograms of dithiocarbonic anhydride when slowly adding 25.0 kilograms of 40.0%NaOH solution then, after the reaction 2.0, be warming up to 50 ℃, continue reaction 4.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, and gets chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 5.7mmol/g in the product of the present invention, and relative molecular mass is 15000～25000, and massfraction is that 1.0% o'clock pH value of solution value is 9.5, and solution density is 1.23g/L.
Embodiment 3: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extract in alkaline process bamboo and the bagasse black liquor, bamboo and bagasse mass ratio are 3: 1): 15.0 kilograms
Formaldehyde (massfraction is 40.0%): 22.0 kilograms
Quadrol: 9.0 kilograms
Dithiocarbonic anhydride: 15.0 kilograms
Sodium hydroxide (massfraction is 50.0%): 18.0 kilograms
Water: 21.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 15.0 kilograms of alkali lignins and 21.0 kg water are added in the reactor, after stirring, with 20.0% sodium aluminate solution the pH value of reaction system is transferred to 11.5, add 22.0 kilograms of formaldehyde behind the heat temperature raising to 65 ℃, add 9.0 kilograms of quadrols behind the reaction 30min, continue to be cooled to 5 ℃ behind the reaction 4.0h, drip 15.0 kilograms of dithiocarbonic anhydride when slowly adding 18.0 kilogram of 50.0% sodium hydroxide solution then, behind the reaction 2.0h, be warming up to 75 ℃, continue reaction 1.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, and gets chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 4.3mmol/g in the product of the present invention, and relative molecular mass is 5000～10000, and massfraction is that 1.0% o'clock pH value of solution value is 9.6, and solution density is 1.21g/L.
Embodiment 4: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extracting in the sulphate process wheat straw black liquor): 11.0 kilograms
Paraformaldehyde 96: 7.0 kilograms
Diethylenetriamine: 8.0 kilograms
Dithiocarbonic anhydride: 12.0 kilograms
Potassium hydroxide (massfraction is 50.0%): 20.0 kilograms
Water: 42.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 11.0 kilograms of alkali lignins and 42.0 kg water are added in the reactor, after stirring, with 50.0%KOH solution the pH value of reaction system is transferred to 10.5, add 7.0 kilograms of Paraformaldehyde 96s behind the heat temperature raising to 90 ℃, add 8.0 kilograms of diethylenetriamines behind the reaction 30min, continue to be cooled to 20 ℃ behind the reaction 2.0h, drip 12.0 kilograms of dithiocarbonic anhydride when slowly adding 20.0 kilogram of 50.0% potassium hydroxide solution then, behind the reaction 4.0h, be warming up to 60 ℃, continue reaction 2.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, filter, and get chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 3.9mmol/g in the product of the present invention, and the solubleness when relative molecular mass is 5000～10000,28.0 ℃ is 41.0g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 9.5, and solution density is 1.17g/L.
Embodiment 5: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extracting in the alkaline process reed pulp black liquor): 5.0 kilograms
Formaldehyde (massfraction is 37.0%): 20.0 kilograms
Urea and hexamethylenetetramine mixture (mass ratio is 1: 1): 15.0 kilograms
Dithiocarbonic anhydride: 18.5 kilograms
Sodium hydroxide (massfraction is 60.0%): 25.0 kilograms
Water: 16.5 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 5.0 kilograms of alkali lignins and 16.5 kg water are added in the reactor, after stirring, with 35.0% sodium acetate soln the pH value of reaction system is transferred to 9.5, add 20.0 kilograms of formaldehyde behind the heat temperature raising to 65 ℃, add 15.0 kilograms of ureas and hexamethylenetetramine mixture behind the reaction 10min, continue to be cooled to 10 ℃ behind the reaction 5.0h, drip 18.5 kilograms of dithiocarbonic anhydride when slowly adding 25.0 kilogram of 60.0% sodium hydroxide solution then, behind the reaction 2.5h, be warming up to 50 ℃, continue reaction 3.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, and gets chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 5.3mmol/g in the product of the present invention, relative molecular mass is 5000～12000,28.0 ℃ the time solubleness be 38.5g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 10.0, and the solution density of massfraction 40% is 1.24g/L.
Embodiment 6: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extracting in the alkaline process eucalyptus pulp black liquor): 20.0 kilograms
Formaldehyde (massfraction is 40%): 10.0 kilograms
Quadrol and tetraethylene pentamine mixture (mass ratio is 4: 1): 10.0 kilograms
Dithiocarbonic anhydride: 15.0 kilograms
Sodium hydroxide (massfraction is 50.0%): 25.0 kilograms
Water: 20.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 20.0 kilograms of alkali lignins and 20.0 kg water are added in the reactor, after stirring, with 50.0%NaOH solution the pH value of reaction system is transferred to 11.5, add 10.0 kilograms of formaldehyde behind the heat temperature raising to 95 ℃, add 10.0 kilograms of quadrols and tetraethylene pentamine mixture behind the reaction 30min, continue to be cooled to 25 ℃ behind the reaction 3.5h, drip 15.0 kilograms of dithiocarbonic anhydride when slowly adding 25.0 kilogram of 50.0% sodium hydroxide solution then, behind the reaction 2.0h, be warming up to 55 ℃, continue reaction 2.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, and gets chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 3.2mmol/g in the product of the present invention, relative molecular mass is 20000～30000,28.0 ℃ the time solubleness be 41.0g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 9.8, and the solution density of massfraction 40% is 1.21g/L.
Embodiment 7: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Xylogen (extracting in the alkaline process masson s pine pulp black liquor): 9.0 kilograms
Trioxymethylene: 2.0 kilograms
Urea: 8.0 kilograms
Dithiocarbonic anhydride: 8.0 kilograms
Sodium hydroxide (massfraction is 20.0%): 25.0 kilograms
Water: 48.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 9.0 kilograms of alkali lignins and 48.0 kg water are added in the reactor, after stirring, with 20.0%NaOH solution the pH value of reaction system is transferred to 11.5, add 2.0 kilograms of trioxymethylenes behind the heat temperature raising to 85 ℃, add 8.0 kilograms of ureas behind the reaction 25min, continue to be cooled to 25 ℃ behind the reaction 2.5h, drip 8.0 kilograms of dithiocarbonic anhydride when slowly adding 25.0 kilogram of 20.0% sodium hydroxide solution then, behind the reaction 2.0h, be warming up to 75 ℃, continue reaction 2.0h, cooling discharge, prepared product are the chocolate thick liquid.After testing, the content of dithiocar-bamate group is 2.6mmol/g in the product of the present invention, and the solubleness when relative molecular mass is 15000～20000,28.0 ℃ is 36.6g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 10.2, and solution density is 1.17g/L.
Embodiment 8: the concrete steps of present embodiment are as follows:
1. the raw material of present embodiment and prescription (unit-kilogram):
Alkali lignin (extracting in the alkaline process birch pulp black liquor): 5.0 kilograms
Formaldehyde (massfraction is 35.0%): 15.0 kilograms
Urea, hexamethylenetetramine and diethylenetriamine mixture (mass ratio is 8: 1: 1): 10.0 kilograms
Dithiocarbonic anhydride: 15.0 kilograms
Sodium hydroxide (massfraction is 50.0%): 20.0 kilograms
Water: 35.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 5.0 kilograms of alkali lignins and 35.0 kg water are added in the reactor, after stirring, with 50.0%NaOH solution the pH value of reaction system is transferred to 11.0, add 15.0 kilograms of formaldehyde behind the heat temperature raising to 75 ℃, add 10.0 kilograms of ureas behind the reaction 10min, hexamethylenetetramine and diethylenetriamine mixture, continue to be cooled to 0 ℃ behind the reaction 4.5h, drip 15.0 kilograms of dithiocarbonic anhydride when slowly adding 20.0 kilogram of 50.0% sodium hydroxide solution then, behind the reaction 2.0h, be warming up to 50 ℃, continue reaction 4.0h, cooling discharge, prepared product is the chocolate thick liquid, or the chocolate thick liquid is concentrated through underpressure distillation, filter, and get chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 5.1mmol/g in the product of the present invention, relative molecular mass is 35000～450000,28.0 ℃ the time solubleness be 35.2g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 9.3, and the solution density of massfraction 40% is 1.23g/L.
Embodiment 9: the concrete steps of present embodiment are as follows:
1. raw material and prescription (massfraction):
Alkali lignin (extracting in the alkaline process masson s pine pulp black liquor): 2.5 kilograms
Formaldehyde (massfraction is 37.0%): 5.0 kilograms
Urea: 20.0 kilograms
Dithiocarbonic anhydride: 27.5 kilograms
Sodium hydroxide solution (massfraction is 50%): 35.0 kilograms
Water: 10.0 kilograms
2. processing step and processing parameter
Preparation of the present invention is carried out under normal pressure:
Earlier 2.5 kilograms of alkali lignins and 10.0 kg water are added in the reactor, after stirring, with strong aqua the pH value of reaction system is transferred to 10.5, add 5.0 kilograms of formaldehyde behind the heat temperature raising to 85 ℃, add 20.0 kilograms of ureas behind the reaction 15min, continue to be cooled to 20 ℃ behind the reaction 2.5h, drip 27.5 kilograms of dithiocarbonic anhydride when slowly adding 35.0 kilogram of 50% sodium hydroxide solution then, behind the reaction 3.0h, be warming up to 50 ℃, continue reaction 1.5h, cooling discharge, prepared product concentrates through underpressure distillation, and gets chocolate brown powder with the acetone crystallization.After testing, the content of dithiocar-bamate group is 6.0mmol/g in the product of the present invention, relative molecular mass is 25000～35000,28.0 ℃ the time solubleness be 35.7g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 10.3, and the solution density of massfraction 40% is 1.24g/L.
The Infrared Characterization of modified lignin oil removing flocculant:
Concentrate, filter by underpressure distillation with the liquid product among the embodiment 3, get chocolate brown powder with the acetone crystallization, utilize the methyl alcohol precipitating again, and be dried to weight with ether recrystallization final vacuum, adopt the KBr pressed disc method, utilize Nicolet AVATAR 360 type Fourier transformation infrared spectrometers to detect acquisition table 1 data.
The infrared spectra spectrum analysis of table 1 modified lignin oil removing flocculant
| Sample | Vibration mode | Absorption peak position (cm -1) | Intensity |
| Embodiment 3 products | v (O-H) v (C＝O) v (C-N) v (C＝S) v (C-S) | 3325 1638 1412 990 782 | S S S S S |
Result from table 1 is as can be known: modified lignin oil removing flocculant is at 3325cm
-1And 1638cm
-1V appears respectively in the place
(O-H)And v
(C=O)Charateristic avsorption band; At 1412cm
-1, 990cm
-1And 782cm
-1V appears in the place
(C-N), v
(C=S)And v
(C-S)Charateristic avsorption band, illustrate that modified lignin oil removing flocculant contains the dithiocar-bamate group, the synthesis technique of product is feasible.
The application of modified lignin oil removing flocculant in oily(waste)water is handled:
The water-quality guideline of table 2 oily(waste)water
| Water-quality guideline | ρ (oil) (mg/L) | ρ(SS) (mg/L) | ρ(COD Cr) (mg/L) | ρ (colourity) (C.U) |
| Gas well waste water changes well waste water | 356.8 489.6 | 509.2 756.3 | 2351.0 3265.2 | 8762 9653 |
The treatment effect of table 3 modified lignin oil removing flocculant
| Product | ρ (clearance)/% | |||||||
| Gas well waste water | Change well waste water | |||||||
| Oil | SS | Colourity | COD Cr | Oil | SS | Colourity | COD Cr | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 | 91.1 93.2 88.7 87.5 94.3 90.5 88.0 89.4 95.5 | 93.1 95.5 90.3 89.6 96.7 93.2 90.6 92.3 97.8 | 89.0 90.2 87.5 90.3 87.5 91.0 88.0 91.1 90.3 | 73.0 75.2 70.1 73.5 75.0 73.2 70.0 72.3 75.5 | 92.3 93.9 89.5 87.1 95.6 91.3 89.7 89.2 96.3 | 92.6 93.8 90.0 87.2 96.1 91.7 87.1 95.2 96.9 | 82.2 89.5 80.0 89.3 87.1 88.6 80.5 87.8 89.0 | 75.0 74.5 67.2 73.0 70.6 71.8 65.5 70.0 74.3 |
Annotate: adopt the beaker laboratory method.The consumption of oil removing flocculant is 35mg/L.
The treatment effect of the different dithiocar-bamate type of table 4 medicament relatively
| Degreaser | ρ (consumption) (mgL -1) | ρ (clearance)/% | |||||||
| Gas well waste water | Change well waste water | ||||||||
| Oil | SS | Colourity | COD Cr | Oil | SS | Colourity | COD Cr | ||
| Embodiment 5 PTC ATC | 35 35 35 | 94.3 91.0 95.0 | 96.7 92.1 96.5 | 87.5 83.0 85.6 | 75.0 71.6 73.8 | 95.6 92.7 95.5 | 96.1 91.8 96.1 | 87.1 85.6 88.2 | 70.6 65.7 71.5 |
Annotate: PTC is a nabam; ATC is dimethylene two (nabam).
From the data of table 2-table 4 as can be known, modified lignin oil removing flocculant of the present invention has good oil removing flocculating effect, and with the treatment effect of existing dithiocar-bamate type medicament relatively, cost performance is more superior.
Claims (8)
1. modified lignin oil removing flocculant, it is characterized in that described modified lignin oil removing flocculant contains the dithiocar-bamate group, the content of dithiocar-bamate group is 2.0～6.7mmol in every gram modified lignin oil removing flocculant, the modified lignin oil removing flocculant relative molecular mass is 5000～50000, be chocolate thick liquid or chocolate brown powder, the solubleness of chocolate brown powder in the time of 28.0 ℃ is 35.0～45.0g/100g water, massfraction is that 1.0% o'clock pH value of solution value is 9.0～10.5, and the solution density of massfraction 40% is 1.16～1.25g/L.
2. the preparation method of the described modified lignin oil removing flocculant of claim 1, its step is as follows: earlier xylogen and water are added in the reactor, after stirring, the pH value of reaction system is transferred to 9.5～11.5, add aldehyde compound behind heat temperature raising to 65～95 ℃, add nitrogenous compound behind reaction 10～30min, continue to be cooled to 0～25 ℃ behind reaction 2.0～5.0h, drip dithiocarbonic anhydride when slowly adding alkali lye then, behind reaction 2.0～4.0h, be warming up to 50～75 ℃, continue reaction 1.0～4.0h, cooling discharge, prepared product are the chocolate thick liquid, and above-mentioned preparation is to carry out under normal pressure.
3. the preparation method of modified lignin oil removing flocculant according to claim 2 is characterized in that comprising the starting material of following massfraction proportioning:
Xylogen: 2.5～20.0%;
Aldehyde compound: 2.0～25.0%;
Nitrogenous compound: 8.0～25.0%;
Dithiocarbonic anhydride: 10.0～30.0%;
Alkali lye: 3.0～40.0%;
Water: 10.0～50.0%.
4. according to the preparation method of claim 2 or 3 described modified lignin oil removing flocculants, it is characterized in that: prepared chocolate thick liquid concentrates, filters through underpressure distillation, and gets chocolate brown powder with the acetone crystallization.
5. according to the preparation method of claim 2 or 3 described modified lignin oil removing flocculants, it is characterized in that the xylogen that uses is alkali lignin, the alkaline process or the kraft process black liquor of the mixed raw material of two or more that starting material are selected from that bamboo, bagasse, straw, wheat straw, reed, Eucalyptus, birch, Pinus massoniana Lamb starting material or its form according to a certain ratio are by precipitation, separate, extract and obtain alkali lignin.
6. according to the preparation method of claim 2 or 3 described modified lignin oil removing flocculants, it is characterized in that the nitrogenous compound that uses is one or both or two or more mixtures in urea, quadrol, diethylenetriamine, tetraethylene pentamine, hexamethylenetetramine, the diethylenetriamine.
7. according to the preparation method of claim 2 or 3 described modified lignin oil removing flocculants, it is characterized in that the alkali lye that uses is sodium hydroxide or potassium hydroxide aqueous solution, and the massfraction scope of alkali lye is 20.0～60.0%.
8. according to the preparation method of claim 2 or 3 described modified lignin oil removing flocculants, it is characterized in that the aldehyde compound that uses is formaldehyde, trioxymethylene or Paraformaldehyde 96.
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| CN104250381B (en) * | 2013-06-26 | 2017-09-12 | 通用电气公司 | Polymer available for water process |
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| CN106565007A (en) * | 2016-11-09 | 2017-04-19 | 烟台史密得机电设备制造有限公司 | Ternary compound flooding produced water deoiling agent and preparation method thereof |
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