TW526255B - Composition of an anti-scale-forming agent - Google Patents

Abstract

A composition for an anti-scale-forming agent includes oil-based polyalkylenes, amines and phosphor in a polymer for providing dispersivity and anti-oxidization. By integrating both characteristics into a single polymer, the anti-scale-forming agent in accordance with the present invention can be used as an excellent anti-scale-forming agent for a manufacturing process in a petroleum refinery plant or the like chemistry factory.

Description

526255 _Case No. η Modification_ V. Description of the Invention (1) Field of the Invention The present invention relates to a composition that has fouling dispersibility and anti-oxidation properties, and particularly relates to the use of additives added to the manufacturing process of chemical products, which can be applied to Heat exchangers, power plants, refineries and other chemical plants (Heat Exchanger), reactors (Reactors) and distillation towers (Disti Hation Tower), and other similar equipment and industry. BACKGROUND OF THE INVENTION Antifouling agents are special-purpose plants, petrochemical intermediates such as bio-deethylene, etc.) their hydrogen compounds, through oxidation furnace wall, long-term accumulation of sewage channels and heat transfer, etc., form a low production capacity, so special chemicals for anti-fouling Product. One kind of chemistry, general real estate and oil refining process (including temperature up to 200 ~ 500t: Pollution caused by polymerization will affect the flow of the process, the source will be wasted and the shutdown agent must be added. The chemical Wei Jing is used in petrochemical and Refining petroleum is cracked, reorganized, and the charcoal in the reaction furnace accumulates in pipelines and even blocks valves and pipes for cleaning, which leads to reduced use and is very important. The generation of accumulations is the style

Impurities or hydrocarbons themselves: Seemingly, the source of the sediment is usually a mechanism that generates polymer polymerization; as it enters, the chemical reaction is caused by the deacidification of free radicals and coke, and if it is two, it is cracked into as Colloids or accelerated free radicals are more serious: Impurities (especially Cu, Fe) activators and metal deactivators, which = f, antifouling agents are usually good resistance to different raw material processing, and f It is widely used in the process of petrochemical industry product control. US Patent No. 4,775,495 is a heteroemulsification method, and US Patent No.

526255

V. Description of the invention (2) ^ 836, 5, 226, 1 86 also describes the applicable number of oxygen in various processes and the principle of interfacial dispersion in order to obtain a more economical method. SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling agent composition, which has fouling dispersibility and antioxidant properties, and the dispersibility is derived from the lipophilic / hydrophilic balance interface agent dispersion principle in the molecular formula. The combination of properties on a molecule 'can be used as an excellent antifouling agent, but can be used in oil refining and other chemical processes' to provide anti-oxidation and anti-fouling effects. In order to achieve the above-mentioned object of the present invention, the composition of the antifouling agent of the present invention includes polyalkylene, amine and phosphonium (PON) on the same molecule, so that it has fouling dispersibility and oxidation resistance. Chemical formula: (RlR2) xP0RVx where 1 ^ and 1 ^ are respectively selected from oligomeric olefins (1) 〇17 & 11 ^ 16116), polyether polyamines (poly ether amine) or oxyakle ne ) Polyamines; 0-based oxygen; P-based phosphorus; X-based 1 or 2. During implementation, the above chemical formula (RiR2) xP〇RYx may have the following structure: 〇 〇 r ^ nh- -L \

R3 = a 1ky1, e.q. po1y i sobu ty1eney1 R4 = poly (oxyalkyl), e. Q. Poly (oxypropylene)

Page 7 526255 _case number fiQlIRQfin_ year month day _____ 5. Description of the invention (¾ X = 1 or 2 and (A) is manufactured by the following program: H2N -R4 -NH2 + P0C13--P4 NH -R2 -NH2) 3 .............. (b)

II 0 (B) + PIBSA-> (A) Different mole ratios Note: PIBSA-Polyisobutylene Succinic anhydride The main steps (technical means) of the method of the present invention are as follows: Select olefins (petrochemical intermediates) via Polyolefins generated by the polymerization reaction are derivatized into acid anhydrides and reacted with phosphinoylamines to form addition products; these products are highly oil-soluble and have at least diamine groups (chelating effect) and phosphorus groups (antioxidant Nature), its specificity and novelty are two kinds of properties on the same molecular structure, so it can be used as an excellent antifouling agent, and used in refineries and other chemical plants. Detailed description of the embodiments of the invention As stated above, the present invention is directed to antifouling agents with good oxidation resistance and antifouling properties, and has the same molecular structure as oily polymers such as olefins, amines, and fillers. The nutrient-polymerized olefins have a disc group (antioxidant properties), and the amines have an amino group (chelation ability), so that one molecule at the same time

Page 8 526255

It has the product of bulkiness and anti-oxidation, so it can be used as an excellent antifouling agent. In the present invention, the polymerized olefins may be olefins, which are formed into oily polymerized olefins through the reaction, and have a molecular weight of about 600 or more and 3, and ~ preferably about 600 to about 150, The preferred polymeric olefins are polyisobutylene (PIB). In the present invention, the amines can be polyether polyamines or poly (oxyalkylene) amines with alkenyloxy groups, and are amines having mono-, di-, tri-, and polyfunctional groups. The class may be selected, for example, from the following:

a. H2NCH2CH2NH2 (ethylene diamine, EDA), b · H2N (CH2) 5NH2 (1,6-diamino hexane), c · H2N (CH2) 2NH (CH2) 2NH2 (diethylenetriamine, DETA), d. H2NC (CH3) HCH2 (0CH2C (CH3) H) xNH2 (X = 2 ~ 3, D-230), e · H2N (CH2) 2NH (CH2) 2NH (CH2) 2NH2 (triethyleneteramine, TETA),, f · (CH3CH2) 2N (CH2 ) 3NH3 (N, N-diethy 1 -1,3-propane diamine), g · H2N (HC (CH3) H2C0) xH2C2- (CH2- (0CH2C (CH3) H) x-NH2) 2C2H5, h. H2N ( CH2CH2〇) 2CH2CH2NH2, i · (CH3) 2N (CH2) 3NH2 (N, N-dimethyl-1,3-propane diamine); amines have a molecular weight of at least about 2 0 or more, and preferably about 2 0 0 To about 200 0. The preferred structure of the antifouling agent used herein is represented by the following k:

Page 9 526255 Case No. 89115960 _ Amendment V. Description of Invention (5)

PnJ CH2CHNl

) H NH (CHCH2〇hCH2a Is y 3-x

R3 = PIB R5 = H, CH3 or C2H5 x = 1 or 2

In the above formula, this chemical structural formula coexists with poly (oxy-alkylene) amine, a PIB group, and a phosphorus chemical group. A synthetic method that can be used in the present invention is the coupling of POC13 with polyetheramine and removal of HC1 to obtain a conjugate. The raw material polyisobutylene Isobutylene (petrochemical intermediate) has a molecular weight of at least about 800 to Polyisobutylamidine (piB) of 2000, and then a polyisobutylamidine-succinic anhydride (PIB-SA) having a molecular weight of about 300 to about 2000 was synthesized by reacting the §11 coupling compound with polyisobutylene-broken acid Sf ( PIB-SA) reaction to obtain the final product (please refer to FIG. 1, a schematic diagram of the process of one embodiment of the antifoulant of the present invention and the chemical formula of the reaction). The novel antifouling agent of the present invention can be applied to the heat exchangers, reactors and distillation towers of any power plant and chemical plant, and uses the test method of atsM D3241 'in Within the scope of the present invention, various new antifouling agents are developed to suit different additives fed by various plants. The effects and benefits of various aspects of the present invention and specific embodiments will be described below.

Page 10 526255 __ 号 号 阁 115960_ 年 Month, Day, Amendment_ V. Description of the Invention (6) The examples are further exemplified, in which the embodiments use the following test procedures. Experimental example:

Dissolve POCl3 (5.4g, 0 · Ό35 mole) and polyetherdiamine (24.15g, 0 · 105 mole) with twice the amount of THF, and drop POC13 into the polyetherdiamine at room temperature. The process is exothermic About 10 ° C. The temperature was heated to 60 ° C and reacted for 4 hours. The THF was concentrated under reduced pressure at room temperature to remove THF, and the concentrated S amp 1 e was dissolved in CHC13. Aqueous NaHC03 solution was added to neutralize HC1 generated during the reaction. The lower organic layer was concentrated under reduced pressure to remove CHC13 to obtain the intermediate product (code B1). 'PIB-SA (11.02 g, 0.0099 1 mole) was taken in a three-necked flask, and then B1 (4.8532 g' 0.00612 mole) was added. ) And excess To 1 uene. When the solvent 'is stirred and heated to 100 ° C for 4 hours, it is taken out under reduced pressure and concentrated to remove Toluene to obtain the final product' FT-IR identification. The result is at 60. 〇 At the reaction temperature, the sample was identified by FT-IR as 〇 = p — n — Η has 1020.4c πΓ 丨 and 907 · 1 cm 1 and 1 59 2 · 2cm · 1 triple absorption peaks. In the second step 1 〇〇 . Hours are 1641.90: 111 and 1545.3 (: 111 " * 丨 (weak) absorption is human 111] ^ 3 (: 丨 (1, also known that the IR absorption of raw materials is 1786.0cm (strong) and 1862.2cm1 (weak)) The double absorption peak has completely disappeared and it is known that the reaction is complete.

The following test procedures are used to determine and evaluate the analytical properties of the antioxidants used in the following examples. The Δ 芩 of the anti-oxidant used in the following examples (indicating the Δ T value after the addition of the antioxidant) was measured according to the test procedure described in ASTM D 3 2 41. Table 1 shows the anti-fouling products with different compositions. The synthetic experimental environment is the product's antioxidant effect within 3 hours at a temperature of 80C (astm D3241)

Page 11 526255

Case number V. Description of the invention (7) Test method) and acid-base titration values of primary, secondary and tertiary amines. Among them, pcp and dcp have phosphorus groups, and polyether diamine (D-23〇, see Figure 1) and phenylenediamine (Phenylene diamine) have amino groups. From the results, it can be found that comparing A1 with A3 or A2 Compared with A4, a composition containing D-230, which has the characteristics of primary and secondary amines, 'has a better ability to couple; also found the data of D-23 with amino groups and stupid diamine, comparing A1 and A3, the results It was found that the antioxidant with D-23G has a higher temperature difference than the antioxidant with phenylenediamine, so the effect of A1 with D-23q is better. One of the test results applicable to the scope of the present invention is shown in Fig. 2. The test disturbance is at a pressure of 500 psi and a temperature of 371. (: At the time of adding I50ppm antioxidant, the flow rate of added antioxidant is 15cc / min. It can be seen from the results that during the processing of crude oil, the temperature difference will increase with time. After adding antioxidant B1, With the increase of time, the temperature difference of crude oil is significantly reduced, and the disadvantages of fouling and excessive oxidation due to the increase of experimental time are controlled. Another test result is shown in Figure 3, which is based on crude oil and the addition of other antifouling agents and the resistance of the present invention The test comparison of the agents, the test environment at a pressure of 500psi and a temperature of 371 ° C, i50ppm antioxidant is added, the flow rate of the added antioxidant is 1.5CC / min, the antifouling agent product A 3 in the scope of the present invention , Reduce the temperature difference of crude oil without adding antifouling agent, but has not yet reached the effect of commercial antifouling agent 'but the black of the festival of this invention _ to. _ Industrialized antifouling agent grade even agent A1, the effect has reached Compared with ί = 较 = antioxidant, ☆ should be found in different preparations and suitable antioxidants, to facilitate the control of temperature and oxidation resistance, can be used in power plants, refineries and other chemicals Plant heat exchanger

526255

Exchanger), reactors (Reactors) and distillation towers (Distiiiation Tower) 'and other similar equipment and industry. The present invention uses the above-mentioned synthesis examples of various antifouling agents to describe the sun and the moon. The above examples are only used for illustration, and it does not mean that the scope of the present invention can only be made with:. The formula is only applicable and limited. 526255 Case No. 89115960 Amendment Brief Description of the Drawings Table 1 is a comparison table of synthetic examples of phosphorus-containing antifouling agents. FIG. 1 is a schematic view showing the process and chemical equations of an embodiment of the antifouling agent of the present invention. Figure 2 is the test chart of ASTM D32 41 with antifouling agent added. Figure 3 is a comparison of ASTM D3241 test of crude oil with different antifouling agents and commercial antifouling agents.

Page 14 526255

> > CO > ΓΟ > K—1 number cx Ο " υ S 'QS giant. \ FREE A ^ ^ g ^ a PIB-SA / B 3 {POCb / Phenylene diamine (l: 3)} PIB -SA / B 2 {DCP / D-230 (1: 4)} PIB-SA / B 1 (POC13 / D-230 (1: 3)) reactant 0.72: 0.50 1 3.09: 0.69! 4.24: 3.36 _1 11.02 : 4.92 Weight ratio 1.5: 1.0 1.5: 1.0 1.5: 1.0 1.5: 1.0 Molar ratio 80 ° C 3hr 80 ° C 丨 3hr 80 ° C 3hr 80 ° C 3hr Conditions o Theoretical value of amine titration 1 1 1 1 1 1 1 1 0.114 0.56 Total amine 1 1 1 1 1 1 1 1 1 0.114 0.51 1 1 1 1 1 1 1 1 1 1 〇0.05 1 • 1 a 1 1 1 1 o 〇 Dark green viscous clear i Orange transparent color drop 22 ° c Drop 10C ASTM test effect NOTES

Claims (1)

1. An antifouling compound, which includes polyolefin based (polyolene i) and polyamines on the same molecule, so that it has fouling dispersion and oxidation resistance. Its chemical structural formula is: ~ 0 Ί II 0 II Η — R2—N Η-II ~ Pn “L 0” X —R2—NH — where f is selected from polymeric olefins (such as polyisobutyleneyl), and R is selected from polyscales (P〇iyethers) or polyolefin Oxyhydrocarbons (such as polyoxopyroxypropia). 2) If the antifouling compound of item 1 of the patent application scope, its detailed chemical formula is: 〇 3 -PsJ 2o4-ch2chnh ^ nh (chch 2o) -ch2chnh-^ y The above R1 is selected from polyisobutyleneyl molecular weight ranging from 800 to 2000, R3 is selected from hydrogen or methyl or ethyl, and X is 1 or 2; y is an integer from 1 to 20 . 3. The antifouling compound according to item 1 of the patent application range, wherein the antifouling agent is oil-soluble; and according to ASTM D3241, the composition has anti-oxidation and dispersion functions. 4 · The antifouling compound according to item 1 of the patent application scope, wherein the polyamines composed of the antifouling agent are selected from H2NCH (CH3) CH2 (0CH2C (CH3) HxNH2 (x = 2 ~ 3) 526255 〇II Cl——P-Clii CH〇CH + H2NCHCH2 (〇CH20H) xNH2 (x = 2 ~ 3) 1: 3 D-230 2PI South THF 0 60 ° C 4hr H2N-D-230-NH ——P—NH——D-230—NH2 + 3HCI Ah D-230Ah o 〇 o Ju Bing Ting No. 殉 Acid P 酑 -s A H2N—D-230—NH——P—NH——D-230 f | lH nh2 D-230 NH2 n 〇 H〇 || M, N——D-230—NH—p——NH——D-230— NH HO D-230 PIB 〇 fljH2 + Λΐ- 〇, Ding Sheng P old * 〇 D-230-NH〇-P-NH ~ -D-230-NH2 D-230 I NH2 Figure 1