Formulations of random polymers for improving crude petroleum flow

Patent metadata

Field	Value
Publication number	US-9932430-B2
Application number	US-201414563136-A
Country	US
Kind code	B2
Filing date	Dec 8, 2014
Priority date	Sep 22, 2009
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

The present invention is related to the use of formulations of new random copolymers and terpolymers, synthesized by a method of semi continuous emulsion polymerization, and that function as flow improvers, lowering the pour point and reducing the viscosity of Mexicans crude oils, which have gravities within the range of 9 to 30° API.

First claim

What is claimed is:

1. A method for producing random polystyrene-polyacetate polymers, wherein said method comprises a semi-continuous emulsion polymerization in a main reactor by feeding a pre-emulsion of styrene and acetate monomers and a transfer agent from one or several tanks by a respective metering pump, at a reaction temperature in the range between 50 and 95° C., where the feed rate of the pre-emulsion is from 0.003 to 0.009 g/mL*min, where the amount of monomers used is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of the mixture of monomers, wherein the random polymers are copolymers having the following formula:

where:
R 1 , R 2 and R 4 are represented by independent radical groups listed below:
R 1 =C 6 H 5 , CH 3 C 6 H 4 , (CH 3 ) 3 C 6 H 3 , (CH 3 ) 3 C 6 H 2 , (CH 3 ) 3 CC 6 H 4 ;
R 2 =H, CH 3 ;
R 4 =H, CN;
m=from 10 to 700;
n=from 1 to 220.

2. The method of claim 1 , wherein the rate of addition of the preemulsion is from 0.004 to 0.007 g/mL·min, and the amount of monomers used is between 10 and 90 weight %.

3. The method according to claim 1 , wherein m is from 20 to 650 and n is from 10 to 200.

4. The method according to claim 1 , wherein m is from 40 to 620 and n is from 20 to 170.

5. The method according to claim 1 , wherein said random polymer formulation comprises a mixture of copolymers having number average molecular weights ranging between 2,000 to 90,000 Daltons.

6. The method according to claim 1 , wherein said random polymers have number average molecular weights ranging between 5,000 and 80,000 Daltons.

7. A method for producing random polyacrylate-polyacetate polymers, wherein said method comprises a semi-continuous emulsion polymerization process in a main reactor by feeding a pre-emulsion of acrylate and acetate monomers and a transfer agent to the main reactor at a rate of 0.003 to 0.009 g/mL·min, at a reaction temperature of 50 to 90° C., the amount of monomers is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of monomers, wherein said random polymer formulation comprises random copolymers having the formula:

where:
R 2 , R 3 and R 4 are represented by independent radical groups listed below:
R 2 =H, CH 3 ;
R 3 =CH 3 , C 2 H 5 , C 4 H 9 , C 6 H 13 , C 8 H 17 , C 10 H 21 , C 12 H 25 , C 18 H 37 ;
R 4 =H, CN;
u=from 1 to 220; and
v=from 1 to 50.

8. The method according to claim 7 , wherein u is from 10 to 200 and v is from 10 to 40.

9. The method according to claim 7 , wherein u is from 30 to 170 and v is from 15 to 30.

10. The method according to claim 7 , wherein said random polymer formulation comprises a mixture of copolymers having molecular weights ranging between 2,000 to 90,000 Daltons.

11. The method according to claim 10 , wherein said molecular weights range between 5,000 and 80,000 Daltons.

12. A method for producing random polystyrene-polyacrylate-polyacetate terpolymers, wherein said method comprises a semi-continuous emulsion polymerization process in a main reactor by feeding a pre-emulsion of styrene, acrylate and acetate monomers and a transfer agent to the main reactor at a rate of 0.003 to 0.009 g/mL-min, at a reaction temperature of 50 to 90° C., the amount of monomers is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of monomers, wherein said random polymer formulation comprises a random terpolymer having the formula:

where:
R 1 , R 2 , R 3 and R 4 are represented by independent radical groups listed below:
R 1 =C 6 H 5 , CH 3 C 6 H 4 , (CH 3 ) 2 C 6 H 3 , (CH 3 ) 3 C 6 H 2 , (CH 3 ) 3 CC 6 H 4 ;
R 2 =H, CH 3 ;
R 3 =CH 3 , C 2 H 5 , C 4 H 9 , C 6 H 13 , C 8 H 17 , C 10 H 21 , C 12 H 25 , C 18 H 37 ;
R 4 =H, CN;
x=from 2 to 900;
Z=from 1 to 300;
y=from 1 to 226.

13. The method according to claim 12 , wherein x is from 20 to 850, z is from 10 to 235 and y is from 10 to 210.

14. The method according to claim 12 , wherein x is from 25 to 700, z is from 20 to 220 and y is from 20 to 200.

15. The method according to claim 12 , wherein the number average molecular weights are in a range from 1,000 to 140,000 Daltons.

16. The method according to claim 12 , wherein the molecular weights are in number range from 2,000 to 100,000 Daltons.

17. A process for producing a random polymer or copolymer selected from the group consisting of

where:
R 1 , R 2 and R 4 are represented by independent radical groups listed below:
R 1 =C 6 H 5 , CH 3 C 6 H 4 , (CH 3 ) 2 C 6 H 3 , (CH 3 ) 3 C 6 H 2 , (CH 3 ) 3 CC 6 H 4 ;
R 2 =H, CH3;
R 3 =CH 3 , C 2 H 5 , C 4 H 9 , C 6 H 13 , C 8 H 17 , C 10 H 21 , C 12 H 25 , C 18 H 37 ;
R 4 =H, CN;
m=from 10 to 700;
n=from 1 to 220;
u=from 1 to 220;
v=from 1 to 50;
x=from 2 to 900;
y=from 1 to 226;
z=from 1 to 300;
said method comprising the steps of preparing a reaction mixture of monomers selected from the group consisting of acrylate, styrene, and acetate monomers, at least one surfactant, a transfer agent and a buffer solution, and feeding said reaction mixture into a reactor at a temperature of about 50 to 95° C. at a rate of about 0.003 to 0.009 g/ml·min to obtain said random polymer or copolymer,
the reaction mixture including said at least one monomer in an amount of 5 to 95% by weight and the amount of the transfer agent in an amount of up to 12 grams per 100 grams of the at least one monomer, wherein said random polymer is effective in reducing the viscosity and depressing the pour point of crude oil having an API gravity of 9 to 30° API.

18. The method according to claim 17 , wherein said random polymer or copolymer has a molecular weight of about 2,000 to 90,000 Daltons.

19. The method according to claim 18 , wherein
m is 20 to 650;
n is 10 to 200;
u is 10 to 200;
v is 10 to 40;
x is 20 to 850;
z is 10 to 235; and
y is 20 to 200.

20. A method for producing random polystyrene-polyacrylate polymers, wherein said method comprises a semi-continuous emulsion polymerization process in a main reactor by feeding a pre-emulsion of styrene and acrylate monomers and a transfer agent to the main reactor at a rate of from 0.003 to 0.009 g/mL-min, at a reaction temperature of 50 to 90° C., the amount of monomers is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of monomers, wherein said random polymer formulation comprises random copolymers having the formula:
where,

R 1 =C 6 H 5 , CH 3 C 6 H 4 , (CH 3 ) 2 C 6 H 3 , (CH 3 ) 3 C 6 H 2 , (CH 3 ) 3 CC 6 H 4 ;
R 2 =H, CH 3 ;
R 3 =CH 3 , C 2 H 9 , C 4 H 9 , C 6 H 13 , C 8 H 17 , C 10 H 21 , C 12 H 25 , C 18 H 37 ;
p=from 1 to 700;
q=from 1 to 50.

21. The method of claim 1 , wherein said reaction mixture includes a monomer mixture consisting essentially of a styrene monomer selected from the group consisting of styrene, 2,4,6-trimethyl-styren

Assignees

• Mexicano Inst Petrol

Inventors

• Castro Sotelo Laura Veronica
• Flores Oropeza Eugenio Alejandro
• Cendejas Santana Gabriel
• Lozada Y Cassou Marcelo
• Vazquez Moreno Flavio Salvador

Classifications

• C08F212/08

  Styrene · CPC title

• C10L1/143

  mixtures of organic macromolecular compounds with organic non-macromolecular compounds · CPC title

• C10L1/1973

  mono-carboxylic · CPC title

• C10L2230/14

  for improving storage or transport of the fuel · CPC title

• C10L1/1608

  Well defined compounds, e.g. hexane, benzene · CPC title