Process for the treatment of produced water from chemical enhanced oil recovery
The present invention relates to a process for the treatment of water from the production well of chemical enhanced oil recovery (CEOR) extraction. In particular, the process relates to the treatment of produced water with a combination of reagents to clarify the water, the reagents being selected from (i) a dithiocarbamate polymer which is water-soluble and has a molecular weight of 00 or more and (ii) a metal ion selected from the group comprising a cation of a transition metal, aluminium and lead, and an apparatus therefor. The use of such reagents in the clarification of produced water from polymer flood from chemical enhanced oil recovery is also disclosed.
1. A process for the treatment of produced water from polymer flood chemical enhanced oil recovery, said process comprising:
providing produced water ( 110 ) comprising water, an anionic polymer and oil;
first treating the produced water with a first reagent ( 160 ) to provide first treated produced water ( 120 );
second treating the first treated produced water with a second reagent ( 260 ) to provide second treated produced water ( 220 ) comprising water and agglomerates comprising oil, anionic polymer, first reagent and second reagent; and
separating the water and agglomerates of the second treated produced water to provide treated water ( 310 ) and separated agglomerates ( 320 );
wherein, the first and second reagents are added separately so that the first and second treating steps are separated by a period of at least 30 seconds;
the first reagent comprises a water-soluble dithiocarbamate polymer comprising dithiocarbamate groups and dithiocarbamate salt groups and has a molecular weight of 500 or more, and
the second reagent comprises a metal ion selected from the group comprising a cation of a transition metal, aluminum and lead.
2. The process of claim 1 wherein the cation of a transition metal comprises a cation selected from the transition metals of groups 7 to group 12 of the periodic table.
3. The process of claim 2 wherein the cation of the transition metal is selected from one or more of the group comprising Hg(II), Ag(I), Cd(II), Cu(II), Zn(II), Co(II), Ni, Fe(II) and Mn(II).
4. The process of claim 3 wherein the metal ion comprises Fe(II).
5. The process of claim 1 wherein the dithiocarbamate polymer comprises a dithiocarbamate polyamine polymer, wherein the dithiocarbamate polyamine polymer is a polyethylenimine or a copolymer of an acrylic-OH or an acrylic-OR 4 monomer and a polyamine monomer in which R 4 is a hydrocarbon group having from 1 to 10 carbon atoms or a NHR 5 group or OR 4 together is a salt of a hydroxyl group, or a dithiocarbamate polyimide polymer, wherein from 5 to 100 mole % of the —NH groups are converted to dithiocarbamate and dithiocarbamate salt groups.
6. The process of claim 5 , wherein from 5 to 50 mole % of the —NH groups are converted to dithiocarbamate and dithiocarbamate salt groups.
7. The process of claim 1 wherein the dithiocarbamate polymer is added in an amount of 0.9 to 2.5 mole equivalents based upon the metal ion.
8. The process of claim 1 wherein the separating step ( 300 ) comprises mechanically separating the second treated produced water.
9. The process of claim 8 wherein the mechanical separation ( 300 ) is carried out using one or more of a hydrocyclone, a corrugated plate interceptor, a compact flotation unit and a gas flotation unit.
10. The process of claim 1 , further comprising, between the first and second treating steps, an intermediate separating step ( 200 ) of:
separating a portion of the oil from the first treated produced water.
11. The process of claim 10 wherein the intermediate separating step ( 200 ) is carried out using a hydrocyclone and optionally gas bubbles.
12. The process of claim 1 wherein the produced water ( 110 ) is provided by the steps of:
providing a polymer flood ( 90 ) from a production well, said polymer flood comprising water, an anionic polymer and crude oil; and
separating the polymer flood to provide recovered crude oil ( 130 ) and the produced water ( 110 ) comprising water, an anionic polymer and oil as residual oil.
13. The process of claim 1 wherein the metal ion comprises Fe(II), the dithiocarbamate polymer comprises a dithiocarbamate polyamine polymer, wherein the dithiocarbamate polyamine polymer is a polyethylenimine or a copolymer of an acrylic-OH or an acrylic-OR 4 monomer and a polyamine monomer in which R 4 is a hydrocarbon group having from 1 to 10 carbon atoms or a NHR 5 group or OR 4 together is a salt of a hydroxyl group, or a dithiocarbamate polyimide polymer, wherein from 20 to 40 mole % of the —NH groups are converted to dithiocarbamate and dithiocarbamate salt groups, and the dithiocarbamate polymer is added in an amount of 0.9 to 2.5 mole equivalents based upon the metal ion.
14. The process of claim 13 , wherein from 25 to 30 mole % of the —NH groups are converted to dithiocarbamate salt groups.