Abstract:
Alkoxylated Mannich product compositions and methods of use of same as process antifoulants are disclosed. The alkoxylated Mannich products deactivate metals and inhibit oxygen promoted polymerization in hydrocarbons and petrochemicals.

Description:
FIELD OF THE INVENTION 
     The present invention pertains to compositions and methods for providing antifouling protection for petroleum hydrocarbons or petrochemicals during processing thereof at elevated temperatures. The compositions and methods also serve to deactivate metals in contact with the aforementioned process streams and to inhibit oxygen based polymerization of certain process fluid constituents. 
     BACKGROUND 
     In the processing of petroleum hydrocarbons and feedstocks such as petroleum processing intermediates, and petrochemicals and petrochemical intermediates, e.g., gas, oils and reformer stocks, chlorinated hydrocarbons and olefin plant fluids such as deethanizer bottoms, the hydrocarbons are commonly heated to temperatures of 100 to 1000° F. (most commonly 500°-1000° F.). Similarly, such petroleum hydrocarbons are frequently employed as heating mediums on the &#34;hot side&#34; of heating and heat exchange systems. In both instances, the petroleum hydrocarbon liquids are subjected to elevated temperatures which produce a separate phase, known as fouling deposits, within the petroleum hydrocarbons. In all cases, these deposits are undesirable by-products. In many processes, the deposits reduce the bore of conduits and vessels to impede process throughput, impair thermal transfer, and clog filter screens, valves and traps. In the case of heat exchange systems, the deposits form an insulating layer upon the available surfaces to restrict heat transfer and necessitate frequent shutdowns for cleaning. Moreover, these deposits reduce throughput, which, of course, results in a loss of capacity with a drastic effect in the yield of finished product. Accordingly, these deposits have caused considerable concern to the industry. 
     Organic foulants are usually higher molecular weight materials ranging in consistency from that of tar to rubber to &#34;popcorn&#34; to &#34;coke.&#34; The exact composition of such foulants is difficult to identify. 
     One particularly troublesome type of organic fouling is caused by the formation of polymers that are insoluble in the hydrocarbon or petrochemical fluid being processed. The polymers are usually formed by reactions of unsaturated hydrocarbons, although any hydrocarbon can polymerize. Generally, olefins tend to polymerize more readily than aromatics, which in turn polymerize more readily than paraffins. Trace organic materials containing hetero atoms such as nitrogen, oxygen and sulfur also contribute to polymerization. 
     Polymers are formed by free radical chain reactions. These reactions, shown below, consist of two phases, an initiation phase and a propagation phase. In reaction 1, the chain initiation reaction, a free radical represented by R°, is formed (the symbol R can be any hydrocarbon). These free radicals, which have an odd electron, act as chain carriers. During chain propagation, additional free radicals are formed and the hydrocarbon molecules (R°) grow larger and larger (see reaction 2c), forming the unwanted polymers which accumulate on heat transfer surfaces. 
     Chain reactions can be triggered in several ways. In reaction 1, heat starts the chain. Example: when a reactive molecule such as an olefin or a diolefin is heated, a free radical is produced. Another way a chain reaction starts is shown in reaction 3. Here, metal ions initiate free radical formation. Accelerating polymerization by oxygen and metals can be seen by reviewing reactions 2 and 3. 
     1. Chain Initiation 
     
         R--H→R°+H° 
    
     2. Chain Propagation 
     
         a. R°+O.sub.2 →R--O--O° 
    
     
         b. R--O--O°+R&#39;--H→R&#39;°+R--O--O--H ##STR1## 
    
     3. Chain Initiation 
     
         a. Me.sup.++ +RH→Me.sup.+ +R°+H.sup.+ 
    
     
         b. Me.sup.++ +R--O--O--H→Me.sup.+ +R--O--O°+H.sup.+ 
    
     4. Chain Termination 
     
         a. R°+R&#39;°→R--R&#39; 
    
     
         b. R°+R--O--O°→R--O--O--R 
    
     Research indicates that even very small amounts of oxygen can cause or accelerate polymerization. Accordingly, to inhibit this insidious fouling problem, it is highly desirable to provide a polyfunctional process antifoulant which can, among other functions, inhibit oxygen based polymerization initiation. This antioxidant function serves as a &#34;chain-stopper&#34; by forming inert molecules with the oxidized free radical hydrocarbons, in accordance with the following reaction: 
     Chain Termination 
     
         ROO°+Antioxidant→ROOH+Antioxidant (-H°) 
    
     
         Antioxidant (-H°)→inert products 
    
     In addition to the desirability of inhibiting oxygen based polymerization, it is highly desirable to inhibit the catalytic formation of gummy deposits and the like which are caused by metallic impurities, such as copper and/or iron, which may be present in the process fluids. These types of antifoulants are referred to as &#34;metals coordinators&#34; or &#34;metal deactivators&#34; and function by forming a complex or ligand with the metallic impurity in the process fluid. 
     Unlike organic deposits, inorganic deposits can be simple to identify. Inorganic deposits include, e.g., metallic salts, oxides, sulfides, etc. of iron, copper and vanadium. Such deposits may be present in the original feed as &#34;ash&#34; or they may be the result of corrosion or precipitation in equipment where fouling is evident. 
     There are many areas in the hydrocarbon processing industry where antifoulants have been used successfully; the main treatment areas are discussed below. 
     In a refinery, the crude unit has been the focus of attention, especially because of fuel cost. Antifoulants have been successfully applied at the exchangers; downstream and upstream of the desalter, on the product side of the preheat train, on both sides of the desalter makeup water exchanger, and at the sour water stripper. 
     Hydrodesulfurization units of all types experience preheat fouling problems. Among those that have been successfully treated are reformer pretreaters processing both straight run and coker naphtha, desulfurizers processing catalytically cracked and coker gas oils, and distillate hydrotreaters. 
     Cat cracker preheat exchanger fouling, both at the vacuum column and at the cat cracker itself, has also been corrected by the use of antifoulants. 
     Chlorinated hydrocarbon plants, such as VCM, EDC and perchloroethane and trichloroethane have also experienced various types of fouling problems. 
     The present invention is directed toward bifunctional anti-foulant methods and compositions which are useful in controlling fouling encountered in petroleum and petrochemical systems as described supra. More specifically, these compositions and methods, due to their bifunctional attributes, may be applied effectively to inhibit fouling caused by oxygen-based free radical formation and/or metal catalysis. 
     SUMMARY OF THE INVENTION 
     In accordance with the invention, metals deactivation and antioxidant activity are demonstrated by the use of certain alkoxylated Mannich products. These alkoxylated Mannich products are formed via reaction of the reactants (A), (B) and (C); wherein (A) is an alkoxylated phenol of the structure ##STR2## wherein R is C 1  -C 10  alkyl, R 1  is selected from alkyl, aryl, alkaryl, or arylalkyl of from about 1 to 20 carbon atoms, x is 0 or 1; (B) is a polyamine of the structure ##STR3## wherein Z is a positive integer, R 2  and R 3  may be the same or different and are independently selected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y may be 0 or 1; and wherein (C) is an aldehyde of the structure ##STR4## wherein R 4  is selected from hydrogen and alkyl having from 1 to 6 carbon atoms. 
     PRIOR ART 
     Schiff bases such as N,N&#39;-salicylidene-1,2-diaminopropane are the most commonly used metal deactivators. In U.S. Pat. Nos. 3,034,876 and 3,068,083, the use of this Schiff base with esters were claimed as synergistic blends for the thermal stabilization of jet fuels. 
     Gonzales, in U.S. Pat. Nos. 3,437,583 and 3,442,791, claimed the use of N,N&#39;-disalicylidene-1,2-diaminopropane in combination with the product from the reaction of a phenol, an amine, and an aldehyde as a synergistic antifoulant. Alone the product of reaction of the phenol, amine, and aldehyde had little, if any, antifoulant activity. 
     Products from the reaction of a phenol, an amine, and an aldehyde (known as Mannich-type products) have been prepared in many ways with differing results due to the method of preparation and due to the exact ratio of reactants and the structure of the reactants. 
     Metal chelators were prepared by a Mannich reaction in U.S. Pat. No. 3,355,270. Such chelators were reacted with copper to form a metal chelate complex which was used as a catalyst for furnace oil combustion. The activity of the copper was not decreased or deactivated by the Mannich reaction chelator. 
     Mannich-type products were used as dispersants in U.S. Pat. Nos. 3,235,484 and Re. 26,330 and 4,032,304 and 4,200,545. A Mannich-type product in combination with a polyalkylene amine was used to provide stability in preventing thermal degradation of fuels in U.S. Pat. No. 4,166,726. 
     We are not aware of any prior art disclosing the preparation of or use of the specific alkoxylated Mannich products as herein disclosed. 
     DETAILED DESCRIPTION OF THE INVENTION 
     We have found that certain alkoxylated Mannich products demonstrate superior antifoulant activity in hydrocarbons and petrochemicals when same are processed at high temperatures (e.g., 100°-1000° F., commonly 600°-1000° F.). These alkoxylated Mannich products are quite versatile in that they function to deactivate metal species and also serve as antioxidants to inhibit oxygen promoted polymerization. 
     Specifically, the alkoxylated Mannich-type products of the invention are formed via reaction of the reactants (A), (B) and (C) wherein (A) is an alkoxylated phenol of the structure ##STR5## wherein R is C 1  -C 10  alkyl, R 1  is selected from alkyl, aryl, alkaryl, or arylalkyl of from about 1 to 20 carbon atoms, x is 0 or 1; (B) is a polyamine of the structure ##STR6## wherein Z is a positive integer, R 2  and R 3  may be the same or different and are independently selected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y may be 0 or 1; and wherein (C) is an aldehyde of the structure ##STR7## wherein R 4  is selected from hydrogen and alkyl having from 1 to 6 carbon atoms. 
     As to exemplary compounds falling within the scope of Formula I supra., p-methoxyphenol (MEHQ) and p-methoxy-o-tert-butylphenol (BHA) may be mentioned. Both of these reactants (A) are commercially available. 
     Exemplary polyamines which can be used in accordance with Formula II include ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like, with ethylenediamine and triethylenetetramine being preferred. 
     The aldehyde component can comprise, for example, formaldehyde, acetaldehyde, propanaldehyde, butrylaldehyde, hexaldehyde, heptaldehyde, etc. with the most preferred being formaldehyde which may be used in its monomeric form, or, more conveniently, in its polymer form (i.e., paraformaldehyde). 
     As is conventional in the art, the Mannich condensation reaction may proceed at temperatures from about 50° to 200° C. with a preferred temperature range being about 75°-175° C. As is stated in U.S. Pat. No. 4,166,726, the time required for completion of the reaction usually varies from about 1-8 hours, varying of course with the specific reactants chosen and the reaction temperature. 
     As to the molar range of components (A):(B):(C) which may be used, this may fall within 0.5-5:1:0.5-5. The preferred range is 2-4:1:2-4. 
     The alkoxylated Mannich product antifoulants of the invention may be dispersed within the hydrocarbon medium within the range of 0.05 to 50,000 ppm based upon one million parts of the hydrocarbon medium. Preferably, they are added in an amount from about 1 to 1,000 ppm. 
     In one typical synthetic procedure, o-t-butyl-p-hydroxyanisole (18.03 g), ethylenediamine (1.5 g), paraformaldehyde (3.3 g), and xylene (75 g) were charged into a three-necked flask and heated to 150° C. The theoretical amount of water was removed by azeotroping by use of a dean-stark trap. After about 3.5 hours, the reaction mixture was cooled. The resulting product contained about 40% alkoxylated Mannich product and about 60% xylene. 
    
    
     EXAMPLES 
     The invention will now be further described with reference to a number of specific examples which are to be regarded solely as illustrative and not as restricting the scope of the invention. 
     Test Methods Utilized 
     Three test methods were employed to show the antifouling versatility of the alkoxylated Mannich products of the invention. These were: (1) hot wire test; (2) oxygen absorption test; and (3) ASTM D-525-80. 
     Hot Wire Test 
     I. Objective: To screen preparations according to the amount of fouling protection they exhibit. 
     II. Method Outline: Samples treated with candidate materials are placed in hot wire apparatus and electrically heated. Fouling deposits from an untreated sample are compared with those of the treatments. 
     Oxygen Absorption Test 
     In the oxygen absorption test, a metal compound, N,N-diethylhydroxylamine (DEHA), a basic amine, and the candidate metal chelator are placed in an autoclave and 50 to 100 psig of oxygen over-pressure is charged to the autoclave. The change in pressure versus time is recorded. With only the metal compound, DEHA, and a basic amine present, absorption of oxygen occurs. A metal deactivator in the reaction will chelate the metal in such a way to inhibit the oxygen absorption. The less the pressure drop, the better the metal deactivator. 
     A typical test used 1.25 g of a 6% copper naphthenate solution, 5.6 g of DEHA, 5.6 g of N-(2 aminoethyl)piperazine, 12.5 g of heavy aromatic naphtha as solvent, and about 2 g of metal chelator. Pressure drops of from 0 to 48 psig were found over a 60 minute time period. With metal species absent, oxygen was not absorbed. 
     ASTM D-525-80 
     In the ASTM test, a sample of a feedstock known to polymerize is placed in an autoclave with a metal compound, an antioxidant, and a metal chelator. An over-pressure of 100 psig of oxygen is added and the apparatus is heated on a hot water bath to 100° C. until a drop in pressure is noted signifying the loss of antioxidant activity. The longer the time until a drop in pressure occurs, the more effective the antioxidant and/or metal deactivator. 
     
                       TABLE I______________________________________Hot Wire and ASTM D-525-80on a Pyrolysis Gasoline Feedstock             Hot Wire Test                          ASTM             (Level Where no                          D-525-80             Deposit      (InductionTest Material     Observed)    Time)______________________________________1.  None              None         15 min.2.  t-butylhydroxyanisole                 240          35 min.    (BHA), triethylene tetra-    mine (TETA), paraformal-    dehyde (PF) 2:1:2 (mo-    lar ratio of reactants)3.  BHA - ethylenediamine                 200          30 min.    (EDA) - PF 2:1:24.  p-methoxyphenol - TETA -                 200          25 min.    PF 2:1:25.  BHA - EDA - PF 4:1:4                 205          40 min.6.  N,N&#39;--disalicylidene-                 200          --    1,2-cyclohexane (com-    mercially available    metal deactivator)(MD)______________________________________ 
    
     
                       TABLE II______________________________________Hot Wire, Oxygen Absorption, ASTM D-525-80Phenol Polyamine Ratio    Amount of Actives______________________________________Hot Wire Data                                ResultNone  None      None     None        7.5 mg avg.Nonyl EDA       4-1-4    220 ppm     3.0 avg.BHA   EDA       4-1-4    200 ppm     0.0Nonyl EDA       2-1-2    220 ppm     2.6BHA   EDA       2-1-2    200 ppm     1.0BHA   TETA      2-1-2    200 ppm     1.0MEHQ  TETA      2-1-2    200 ppm     1.5Oxygen Absorption Data                                ΔpsiNone  None      None     None        48, 48Nonyl EDA       4-1-4    2.0 g       21MEHQ  TETA      4-1-4    2.0 g       20, 17MEHQ  TETA      4-1-4    4.0 g       7Nonyl EDA       2-1-2    2.0 g       17MEHQ  TETA      2-1-2    2.0 g       2, 1.5, 6BHA   EDA       2-1-2    2.0 g       34, 33BHA   EDA       2-1-2    2.5 g       39, 29BHA   TETA      2-1-2    2.3 g       28, 30ASTM D-525 Data                                InductionNone  None      None     None        25, 26 min.Nonyl TETA      1-1-2    200 ppm     27 min.BHA   EDA       2-1-2    200 ppm     81 min.MD    --        --       120 ppm     26 min.______________________________________ BHA = butylated pmethoxyphenol (ot-butyl-p-methoxyphenol) MEHQ = pmethoxyphenol EDA = ethylenediamine TETA = triethylene tetramine 
    
     Additional hot wire tests using 80 ppm of copper naphthenate were undertaken with respect to several of the alkoxylated Mannich products of the invention and several comparative materials. Results are shown in Table III. 
     
                       TABLE III______________________________________      Ratio Phenol-      Ethylenedia-                  ConcentrationMaterial   mine (EDA)-F                  (ppm) Actives                              Coke (mg)______________________________________None       --          --          7.5                              (avg of 6)p-t-butyl- 2-1-2       350         0p-nonyl-   4-1-4       220,220,400,800                              3.1,2.9,1.5,1p-nonyl-   2-1-2       220,400     2.6,1.9p-dodecyl- 4-1-4       520         0p-methoxy-o-t-      4-1-4       200         0butyl-p-methoxy-o-t-      2-1-2       200         1.0butyl-PHENOL-TETA-PARAFORMALDEHYDEp-methoxy- 2-1-2       200         1p-methoxy-o-t-      2-1-2       200         1.5butyl-N,N&#39;--disalicyli-      --          200         0dene-1,2-cy-clohexane______________________________________ 
    
     
                       TABLE IV______________________________________Oxygen Absorption Data                Phenol-Amine-                FormaldehydePhenol       Amine   (Molar Ratio)                            m mols                                  ΔP______________________________________None         None    --          --    48,48N,N&#39;--disalicylidene-                --          2.5   7,51,2-cyclohexanep-nonyl-     EDA     2-1-2       0.8   17,48.sup.a                            2.3   5p-nonyl-     EDA     4-1-4       2.0   6p-methoxy-o-t-butyl-        TETA    2-1-2       1.5   48.sup.a______________________________________ .sup.a Probable leak in autoclave 
    
     Based on the above laboratory data, it is presently preferred to use p-methoxyphenol--triethylenetetramine--PF in a molar ratio of components of 2:1:2. 
     The above data demonstrate the superior antifoulant characteristics of the alkoxylated Mannich products of the invention by reason of the superior performance of the materials in the hot wire tests. The oxygen data indicates that the materials are good metal deactivators, whereas the ASTM 525 test indicates that the materials provide significant antioxidant activity. 
     Reasonable variations and modifications will be apparent to those skilled in the art and can be made without departing from the spirit and scope of the invention.