REDTJCTION OF AMMONIA WASTES

BACKGROUND OF THE INVENTION

This application is a continuation-in-part of United States patent application serial number 08/390,726 filed February 17, 1995 and ccpending herewith.

The invention relates to reduction of ammonia wastes produced in processes for production of acrylonitrile by catalytic ammoxidation of propylene in a fluidized bed reaction.

Commercial processes for production of acrylonitrile by passage of propylene, oxygen (air) , and ammonia through a fluidized bed of aππioxidation catalyst are well known by those skilled in the art. In such processes an excess of ammonia is commonly employed and necessary to obtain high levels of conversion of propylene to acrylonitrile. As a result, significant levels of arrmonia are present in the product stream and must be recovered and/or converted to other waste products such as ammonium nitrates or sulfates at considerable expense.

The addition of methanol to processes of catalytic ammoxidation of propylene to acrylonitrile in order to increase hydrogen cyanide co-product production and, to some extent, consume excess ammonia is known. It is further known that methanol can compete with propylene in aumoxidation reactions and difficulty may be experienced in preventing reduction in acrylonitrile yields.

It will be appreciated by those skilled in the art that processes for reducing amnonia wastes without seriously impairing conversion of propylene to acrylonitrile are desired from the standpoint of both economic and environmental considerations.

- 2 -

SUMMARY OF THE INVENTION

The invention is based on the discovery that in a process for making acrylonitrile by passing propylene, oxygen (air) , and ammonia through a fluidized bed of aimoxidation catalyst, the amount of ammonia contained in the product stream can be effectively and economically reduced without substantial adverse effect on acrylonitrile yield by introducing methanol into the reactor under non-coking conditions at a point and in an amount such that ammonia in the reactor effluent is substantially reduced without undue reduction in acrylonitrile yield. This continuation is particularly directed to the prevention of blockage of the methanol addition means used in the process. The invention will be fully understood from the following description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with this invention, methanol is introduced into a fluidized bed reaction system in which a bed of ammoxidation catalyst is fluidized by a flow of the reactants, propylene, ammonia, and oxygen containing gas (air) . The use of such systems for the manufacture of acrylonitrile is well known. Essentially any of the numerous catalysts known for the airmoxidation of propylene can be employed using conventional ammoxidation reaction conditions. For example, catalysts mainly consisting of bismuth phosphates or molybdates or of antimony and uranium oxides or of bismuth phosphates or molybdates doped with iron, nickel, cobalt etc., or of antimony oxide and oxides of metals such as iron, cobalt, or nickel may be used. A particularly preferred catalyst is represented by the formula in which Me is nickel or cobalt, a is 1 to 10, b is 0.1 to 5, c is 0.1 to 5, d is 0.001 to 0.1, e is 0.001 to .1, f is 0

to 0.1 and g is a number taken to satisfy the valences of the quantities of other components present. Ammoxidation processes using catalysts of this type are described, for example, in U.S. Patents 4,018,712, 4,545,943, and 4,487,850, the disclosures of these patents being incorporated herein by reference.

The methanol will be introduced at a point and in an amount such that the ammonia content of the reactor effluent will be less than 0.5 mole percent and lower than if no methanol were introduced and such that acrylonitrile production measured as weight per unit of time is at least 97% by weight of what would be obtained if no methanol were introduced. Preferably, ammonia effluent will be less than 0.25 mole percent or, most preferably, substantially eliminated with less than 1% reduction in acrylonitrile production.

In a preferred embodiment of the invention, the methanol is introduced into the fluidized bed reactor at a point where 5% to 60% by weight of the catalyst in the reactor is above the methanol introduction point. Such point can be determined by calculational methods well understood by those skilled in the fluid bed art or by actual measurement techniques based, for example, on pressure measurements made at various reactor heights. The weight of the catalyst above the injection point refers to the weight when the bed is fluidized under operating conditions. Also, it is contemplated that the catalyst charge will be an amount chosen to ensure complete ammoxidation of the propylene but without undue excess. The optimum point of introduction may vary depending on how much excess catalyst, if any, is present; catalyst activity; surface area; etc. For any system, the optimum injection point can be determined by routine testing conducted in light of the disclosure herein.

The amount of methanol used will be sufficient to react with a major portion of the ammonia

not reacted with propylene. However it is desirable to avoid excesses of methanol which would be expensive to separate from the acrylonitrile product. Preferably, the methanol content of the effluent will be less than 0.25 mole percent, most preferably, less than 0.01 mole percent. Generally, the use of from 0.8 to 2.0 times the moles stoichiometrically required to react with the ammonia in excess of that required for the anτnoxidation of propylene will give satisfactory results. Like the optimum point of methanol introduction, the amount of methanol to be utilized will depend upon the catalyst in use and the amount present; the quantities of other reactants present; and flow rates in the fluidized bed system. It is preferred to introduce the methanol in a downward direction so that the openings through which it is introduced will not become clogged when the reactor is shut down or methanol flow is stopped for maintenance or other reasons. Since the methanol introduction means will generally be of relatively small dimensions and, more importantly, may not be operated continuously, care should be taken to prevent blockage. It is particularly preferred, in order to prevent clogging or blockage in the sparger, tube, or other means through which methanol is introduced, that a gas flow in addition to methanol be maintained at all times that a catalyst charge is present on the reactor, even if the reactor bed is not fluidized. The gas can be any inert gas which is defined as a gas which will not adversely affect the reaction or reactor materials of construction. For example, nitrogen or carbon dioxide can generally be used at any time. Air can be used in amounts which will not form explosive mixtures with methanol (or in any amount if the reactor is "down" or if methanol is not being introduced into the reaction) . Steam can be conveniently and advantageously used if

the reaction is in progress. Mixtures of gases can be used. The gas flow linear velocity through the orifices of the methanol introduction means should exceed (preferably by ten to fifty times) the linear velocity of other gases through the fluid bed reactor. If the reactor is "down" and no gas flow, for example, from purges of the reactant inlets, is present, it is still desirable to maintain a minimal flow to ensure catalyst fines are not drawn into the methanol introduction means. It is further desirable that the openings in the sparger, tube, or other means through which methanol is introduced be significantly larger than the catalyst particles present in the reactor. More specifically, the diameters of the openings (or smallest dimension of the opening if non-round openings are used) should be at least ten, preferably, at least twenty or thirty times the mean particle size of the largest 10% by weight of the catalyst particles. There is no upper limit on opening size except such as may be dictated by considerations of gas flow patterns and rates which may also render it desirable to decrease the number of openings as opening size increases.

It is known that methanol in contact with iron or iron containing alloys or materials of construction will undergo reactions leading to coking at elevated temperatures such as commonly employed in ammoxidation reactions. In order to minimize down time for cleaning coked reactor inlet lines and spargers, it is important that the methanol be introduced under non- coking conditions. This can be accorrplished by use of non-ferrous or high molybdate containing stainless steel inlet lines and spargers, but the expense may be undesirable. Alternatively, the portion of the inlet line between the reactor inlet point and point of discharge can be insulated to maintain the temperature of the conduit below coking temperature but this is frequently inconvenient and the space occupied inside

the reactor by an insulated conduit may interfere with fluid bed flow patterns. In accordance with the present invention, it is preferred to prevent major coking by vaporizing the methanol prior to the point the methanol inlet line enters the reactor and by locating the inlet line entry point as close to its point of discharge (the sparger) inside the reactor as possible.

In order to prevent coking, it is particularly preferred to mix the methanol with water vapor (steam) and/or air. Steam is preferred in order to prevent the possible formation of combustible or explosive mixtures. Coking can generally be adequately prevented by the use of a mixture of methanol with at least 20 mole percent steam or air or mixture thereof. The use of additional steam or air (or other gas which does not adversely affect the reaction system) may be desirable to provide a volume of gas flow sufficient to assure good distribution of the methanol in the fluid bed system. However, the amount of air, if any, mixed with the methanol should not be so great as to form a flaimiable mixture.

Minor modifications in the primary acrylonitrile process may be desirable to optimize production of acrylonitrile and, if desired, co- products such as hydrogen cyanide. Better hydrogen cyanide yields and less loss of acrylonitrile are experienced if the oxygen (air) to propylene ratio is increased so that the oxygen exiting the reaction is about the same as in the case of the conventional (no methanol present) process for ammoxidation of propylene. The oxygen (air) should be sufficient to prevent catalyst reduction but not so great as to form explosive mixtures. The practice of the invention and its comparison with conventional processes is further illustrated by the following examples.

EXAMPLES I-XVII

In these examples, a 4.1 cm inside diameter by 1.8 meter high fluidized bed reactor constructed of 316 stainless steel is used. The outlet end of the reactor is connected to a gas chromatograph for analysis of effluent gases. Propylene, ammonia and air feeds are supplied via mass flow controllers and are premixed before being brought into contact with the fluidized bed. The methanol is fed separately by a positive displacement pump and is vaporized by heating prior to being introduced into the reactor. The reactor contains the amount shown in Table 1 below of catalyst indicated. Catalyst number 1 has the following composition: SbiU ₀ .ieFe ₀ . ₃₇ Bi. ₀ iMo. ₀₂ O,.

(O _x indicates the elements are present as their oxides and the composition contains sufficient oxygen to satisfy their valences) which is deposited on 50% by weight Si0 ₂ carrier. Catalyst 2 is a mixture of iron and antimony oxides deposited on a silica carrier. Catalyst 3 is a mixture of bismuth, molybdenum, and iron oxides on a silica carrier.

Since catalyst activity may vary somewhat with extended usage, each example compares a limited number of successive runs with methanol in the feed stream against a control in which no methanol is introduced.

In all cases, an inert gas flow through the methanol sparger openings (which are about thirty times the diameter of the mean particle size of the largest 10% by weight of the catalyst particles) at a linear velocity about 30 times greater than the linear velocity of the flow of other gases through the reactor is maintained. No clogging of the sparger is observed. No coking is observed in the examples.

TABLE 1

Example I Example II

CATALYST: r ^~ τ— Γ _MZ_.

REACTOR CONDITIONS :

REACTOR TEMP dag C 458 458 459 459

REACTOR PRESS arms 2.02 2.02 2.02 2.01

METHANOL INJ POINT cms 41.91 41.91 41.91 41.91

WT % of CATALYST ABOVE lha MaOH INJECTION PT. % 3.91 3.91

CATALYST CHARGE g s 340 340 340 340

REACTOR FEEDS :

NH3 FEED MOL/HR 1.427 1.427 1.419 1.419

C3H6 FEED MOUHR 1.299 1.299 1.299 1.299

AIR FEED MOL/HR 14.2S 14.249 14.243 14.243

N2 FEED (w/MaOH) MOUHR 0.387 0.387 0.387 0-387

METHANOL FEED MOL/HR 0.193 0.152

NH3/C3H6 FEED RATIO 1.098 1.098 1.092 1.092

AIR C3H6 FEED RATIO 10.967 10.966 10.961 10.981

M«OH/C3Hβ FEED RATIO 0.148 0.117

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.558 0.156 0.450 0.274 MOLE % 02 in EFFLUENT 3.056 2.640 3.334 3.231 MOLES METHANOL OUT 0.085 0.091 MOLES MaOH FEED /MOLE NH3 IN BC EFFLUENT 1.90 1.85 PROPYLENE CONVERSION mole % 98.751 98.207 98.487 97.904

METHANOL CONVERSION mole % 56.171 40.253

PRODUCT RESULTS and RESULT :

AN MAKE gms/hr 56.378 56.810 56.444 57.327

HCN MAKE gms/hr 6.891 7.198 6.461 7.238

RATIO HCN /AN gms HCN/g AN 0.122 0.127 0.114 0.126

NH3 Breakthrough gms/hr 1.729 0.492 1.393 0.861

NH3 Reduction gms/hr 1.237 0.532

TABLE 1

Example III Example IV

CATALYST: CZ ] I ^ι I

REACTOR CONDITIONS :

REACTOR TEMP deg C 459 459 457 457

REACTOR PRESS atms 2.02 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 33.02 33.02 T % of CATALYST ABOVE the MeOH INJECTION PT. % 3.91 24.29

CATALYST CHARQE gma 340 340 340 340

REACTOR FEEDS :

NH3 FEED MOL/HR 1.418 1.418 1.423 1.423

C3H6 FEED MOLHR 1.299 1.299 1.304 1.305

AIR FEED MOLHR 14.242 14.243 14.24 14.244

N2 FEED (w/MeOH) MOL HR 0.387 0.387 0.387 0.387

METHANOL FEED MOL HR 0.152 0.169

NH3 C3H6 FEED RATIO 1.091 1.091 1.091 1.090

AIR C3H6 FEED RATIO 10.961 10.961 10.917 10.912

MeOH/C3H6 FEED RATIO 0.117 0.130

EFFLUENT CONDITIONS :

MOLE % NH3 In EFFLUENT 0.422 0.143 0.474 0.112 MOLE % 02 In EFFLUENT 3.308 2.988 3.132 2.377 MOLES METHANOL OUT 0.040 0.017 MOLES MeOH FEED /MOLE NH3 IN BC EFFLUENT 1.98 1.96 PROPYLENE CONVERSION mole % 98265 97.452 98.284 97.243

METHANOL CONVERSION mole % 73.824 89.740

PRODUCT RESULTS and RESULT :

AN MAKE gms hr 57.442 57.316 55.694 55.184

HCN MAKE gms/hr 6.472 7.887 6.831 8.720

RATIO HCN /AN gms HCN/gm AN 0.113 0.138 0.123 0.158

NH3 Breakthrough gms/hr 1.306 0.449 1.469 0.353

NH3 Reduction gms/hr 0.857 1.116

TABLE 1

Example V

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 457 458

REACTOR PRESS atma 2.02 2.01

METHANOL INJ POINT cms 33.02 33.02

ATT % of CATALYST ABOVE the MeOH INJECTION PT. % 24.29

CATALYST CHARGE gms 340 340

REACTOR FEEDS :

NH3 FEED MOL/HR 1.422 1.422

C3H6 FEED MOUHR 1.304 1.304

AIR FEED MOUHR 14239 1424

N2 FEED ( /MeOH) MOUHR 0.387 0.387

METHANOL EED MOUHR 0.169

NH3/C3H6 FEED RATIO 1.090 1.090

AIR C3H6 FEED RATIO 10.916 10.917

MeOH/C3H6 FEED RATIO 0.130

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.488 0.119 MOLE % 02 In EFFLUENT 2.926 2.247 MOLES METHANOL OUT 0.009 MOLES MaOH FEED /MOLE NH3 IN BC EFFLUENT 1.91 PROPYLENE CONVERSION mole % 98.464 97.896

METHANOL CONVERSION mole % 94.686

PRODUCT RESULTS and RESULTS :

AN MAKE gms hr S5.280 54.459

HCN MAKE gma/hr 6.961 8.703

RATIO HCN /AN gms HCN/gm AN 0.126 0.160

NH3 Breakthrough gms/hr 1.513 0.375

NH3 Reduction gma/hr 1.138

TABLE 1

Example VI

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 457 457 457 457 456

REACTOR PRESS atms 2.02 2.02 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 41.91 41.91 41.91

WT % of CATALYST ABOVE the MeOH INJECTION PT. % 25.75 25.75 25.75 25.75

CATALYST CHARGE gms 440 440 440 440 440

REACTOR FEEDS :

NH3 FEED MOL/HR 1.427 1.428 1.427 1.427 1.427

C3H6 FEED MOUHR 1.299 1.300 1.300 1.300 1.300

AIR FEED MOUHR 14248 14.249 14.248 14.248 14246

N2 FEED ( /MaOH) MOUHR 0.387 0.387 0.387 0.387 0.387

METHANOL FEED MOUHR 0.199 0.150 0.093 0.249

NH3/C3H6 FEED RATIO 1.098 1.098 1.097 1.097 1.097

AIR C3H6 FEED RATIO 10.965 10.958 10.957 10.957 10.955

MeOH/C3H6 FEED RATIO 0.153 0.115 0.071 0.192

EFFLUENT CONDITIONS :

MOLE % NH3 In EFFLUENT 0.558 0.128 0.133 0250 0.020 MOLE % 02 in EFFLUENT 2.185 1.403 1.556 1.731 1.120 MOLES METHANOL OUT 0.002 0.001 0.001 0.003 MOLES MeOH FEED MOLE NH3 IN BC EFFLUENT 1.95 1.47 0.91 2.45 PROPYLENE CONVERSION mole % 100.000 99.716 99.607 99.795 99.427

METHANOL CONVERSION mole % 99.229 99.237 99292 98.814

PRODUCT RESULTS and RESULTS :

AN MAKE gms/hr 55.312 55.996 54.722 55.274 50.092

HCN MAKE gms/hr 7.229 6.930 B.B59 8.503 8.840

RATIO HCN /AN gms HCN/gm AN 0.131 0.159 0.162 0.154 0.176

NH3 Breakthrough gms/hr 1.734 0.406 0.419 0.784 0.064

NH3 Reduction gms/hr 1.328 1.315 0.950 1.670

TABLE 1

Example VII

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 461 461 461

REACTOR PRESS alms 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 41.91 T % of CATALYST ABOVE the MeOH INJECTION PT. % 14.03 14.03

CATALYST CHARQE gms 380 380 380

REACTOR FEEDS :

NH3 FEED MOUHR 1.425 1.426 1.425

C3H6 FEED MOUHR 1299 1299 1.299

AIR FEED MOUHR 14258 14257 14259

N2 FEED (w/MaOH) MOUHR 0.374 0.374 0.374

METHANOL FEED MOUHR 0.159 0.319

NH3 C3H6 FEED RATIO 1.097 1.098 1.097

AIR C3H6 FEED RATIO 10.977 10.976 10.978

MeOH/C3H6 FEED RATIO 0.122 0245

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.819 0.310 0.037 MOLE % 02 in EFFLUENT 3.645 2.933 2.317 MOLES METHANOL OUT 0.012 0.042 MOLES MeOH FEED /MOLE NH3 IN BC EFFLUENT 1.07 2.14 PROPYLENE CONVERSION mole % 98.705 98249 97.855

METHANOL CONVERSION mole * 92.411 86.732

PRODUCT RESULTS and RESULTS :

AN MAKE gms/hr 54.790 53.652 53.895

HCN MAKE gms/hr 7.307 10.126 10.936

RATIO HCN /AN gms HCN/gm AN 0.133 0.189 0.203

NH3 Breakthrough gms/hr 2.541 0.977 0.118

NH3 Reduction gms/hr 1.564 2.423

TABLE 1

Example VIII Example IX

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 461 462 461 461 460

REACTOR PRESS at a 2.02 2.02 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 41.91 41.91 41.91

WT % of CATALYST ABOVE the MeOH INJECTION PT. % 14.03 14.03 18.33

CATALYST CHARGE gms 380 380 380 400 400

REACTOR FEEDS :

NH3 FEED MOUHR 1.425 1.425 1.425 1.428 1.428

C3H6 FEED MOUHR 1.299 1.299 1.299 1.299 1.299

AIR FEED MOUHR 14258 14257 14.506 14266 14.269

N2 FEED (w/MeOH) MOUHR 0.374 0.374 0274 0.374 0.374

METHANOL FEED MOUHR 0.317 0217 0222

NH3/C3H6 FEED RATIO 1.097 1.097 1.097 1.099 1.099

AIR/C3H6 FEED RATIO 10.977 10.976 11.168 10.983 10.986

MeOH/C3H6 FEED RATIO 0.244 0.244 0.171

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.798 0.000 0.000 0.608 0.120 MOLE % 02 in EFFLUENT 3.442 2.047 2.514 2.904 2.042 MOLES METHANOL OUT 0.102 0.101 0.014 MOLES MeOH FEED /MOLE NH3 IN BC EFFLUENT 2.18 2.18 2.00 PROPYLENE CONVERSION mole % 99.027 98.128 97.790 99.068 98.522

METHANOL CONVERSION mole % 67.946 68.104 93.548

PRODUCT RESULTS and RESULTS :

AN MAKE gma/hr 54.496 54.158 54.079 54.783 54.166

HCN MAKE gma/hr 7.518 10.070 10.146 7.518 9.858

RATIO HCN /AN gma HCN/gm AN 0.138 0.186 0.188 0.137 0.182

NH3 Breakthrough gma/hr 2.477 0.000 0.000 1.689 0.381

NH3 Reduction gma hr 2.477 2.477 1.508

TABLE 1

Example X Example XI

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 460 461 461 460 461

REACTOR PRESS alma 2.02 2.02 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 41.91 41.91 41.91 T % of CATALYST ABOVE the MeOH INJECTION PT. % 18.33 18.33

CATALYST CHARGE gms 400 400 400

REACTOR FEED :

NH3 FEED MOUHR 1.428 1.427 1.428 1.427 1.427

C3H6 FEED MOUHR 1.299 1299 1.299 1299 1.300

AIR FEED MOUHR 14.265 14261 14.318 14.526 14.537

N2 FEED (w/MeOH) MOUHR 0.374 0.374 0.374 0.374 0274

METHANOL FEED MOUHR 0.278 0233 0.333

NH3/C3H6 FEED RATIO 1.099 1.099 1.099 1.099 1.098

AIR/C3H6 FEED RATrO 10.983 10.980 11.023 11.184 11.183

MeOH/C3H6 FEED RATIO 0214 0257 0.256

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.544 0.020 0.020 0.559 0.017 MOLE % 02 In EFFLUENT 2.850 1.761 1.431 2.954 1.594 MOLES METHANOL OUT 0.034 0.000 0.034 MOLES MeOH FEED MOLE NH3 IN BC EFFLUENT 2.80 3.36 3.22 PROPYLENE CONVERSION mole % 99.349 98.457 98.034 99.475 98.271

METHANOL CONVERSION mole % 87.614 100.000 89.923

PRODUCT RESULTS and RESULTS :

AN MAKE gms/hr 55.336 55.762 54.818 54.808 54.54S

HCN MAKE gms/hr 7.414 9.646 10.948 7.512 10.129

RATIO HCN /AN gms HCN/gm AN 0.134 0.173 0200 0.137 0.186

NH3 Breakthrough gms/hr 1.690 0.064 0.064 1.762 0.055

NH3 Reduction gms/hr 1.626 1.626 1.707

TABLE 1

Example XII Example XIII

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 451 449 460 459 459

REACTOR PRESS atms 2.02 2.02 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 41.91 41.91 41.91

WT % of CATALYST ABOVE the MeOH INJECTION PT. % 43.88 26.52 26.52

CATALYST CHARGE gms 650 650 578 578 578

REACTOR FEEDS :

NH3 FEED MOUHR 1259 1.360 1.562 1.562 1.562

C3H6 FEED MOUHR 1299 1299 1299 1299 1299

AIR FEED MOUHR 15.659 15.658 13.312 13.311 13.769

N2 FEED ( /MeOH) MOUHR 0.374 0.374 0.374 0.374 0.374

METHANOL FEED MOUHR 0.278 0.139 0.139

NH3/C3H6 FEED RATIO 1.046 1.047 1.203 1.203 1.203

AIR C3H6 FEED RATIO 12.056 12.055 10249 10.248 10.601

MeOH/C3H6 FEED RATIO 0.214 0.107 0.107

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.577 0.102 0.420 0.140 0.123 MOLE % 02 in EFFLUENT 3.610 2.508 1.242 0.963 1.354 MOLES METHANOL OUT 0.025 0.010 0.023 MOLES MeOH FEED /MOLE NH3 IN BC EFFLUENT 2.47 1.89 1.89 PROPYLENE CONVERSION mole % 98.042 97.109 99.021 98.866 98.782

METHANOL CONVERSION mole % 90.912 92.967 83.701

PRODUCT RESULTS and RESULTS :

AN MAKE gms/hr 54.343 54.198 51.056 50.795 50.515

HCN MAKE gms/hr 5.820 8.699 9.831 11.364 11.247

RATIO HCN /AN gms HCN/gm AN 0.107 0.161 0.193 0.224 0.223

NH3 Breakthrough gms/hr 1.915 0.347 1.249 0.422 0.380

NH3 Reduction gms/hr 1.568 0.827 0.868

TABLE 1

Example XIV Example XV

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP deg C 459 458 460 460

REACTOR PRESS atms 2.02 2.02 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91 41.91 41.91

WT % of CATALYST ABOVE the MeOH INJECTION PT. % 26.52 12.88

CATALYST CHARGE gms 578 578 375 375

REACTOR FEEDS :

NH3 FEED MOUHR 1.562 1.561 1.425 1.426

C3H6 FEED MOUHR 1299 1299 1299 1.299

AIR FEED MOUHR 13.772 14.122 14249 1425

N2 FEED (w/MeOH) MOUHR 0.374 0.374 0.374 0.374

METHANOL FEED MOUHR 0.251 0.139

NH3/C3H6 FEED RATIO 1.203 1202 1.097 1.096

AIR/C3H6 FEED RATIO 10.603 10.873 10.970 10.971

MeOH/C3H6 FEED RATIO 0.193 0.107

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.400 0.000 0.412 0.091 MOLE % 02 in EFFLUENT 1.742 1.311 2.965 2.471 MOLES METHANOL OUT 0.033 0.012 MOLES MeOH FEED MOLE NH3 IN BC EFFLUENT 3.50 1.85 PROPYLENE CONVERSION mole % 99.022 97.927 99.182 98.766

METHANOL CONVERSION mole % 86.828 91.675

PRODUCT RESULTS and RESULTS :

AN MAKE gms/hr 50.627 50.695 55.052 54.489

HCN MAKE gms/hr 10.081 12.155 7220 9.655

RATIO HCN /AN gms HCN/gm AN 0.199 0.240 0.133 0.177

NH3 Breakthrough gms/hr 1.222 0.000 1278 0.286

NH3 Reduction gms/hr 1.222 0.992

TABLE 1

Example XVI

CATALYST:

REACTOR CONDITIONS :

REACTOR TEMP de C 464 463

REACTOR PRESS alms 2.02 2.02

METHANOL INJ POINT cms 41.91 41.91

WT % of CATALYST ABOVE the MeOH INJECTION PT. % 12.88

CATALYST CHARGE gms 375 375

REACTOR FEEDS :

NH3 FEED MOUHR 1.426 1.426

C3H6 FEED MOUHR 1.299 1.299

AIR FEED MOUHR 14.248 14.25

N2 FEED ( /MeOH) MOUHR 0.374 0.374

METHANOL FEED MOUHR 0.195

NH3/C3H6 FEED RATIO 1.098 1.098

AIR/C3H6 FEED RATIO 10.970 10.971

MeOH/C3H6 FEED RATIO 0.150

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.403 0.009 MOLE % 02 in EFFLUENT 3.027 2.204 MOLES METHANOL OUT 0.026 MOLES MeOH FEED /MOLE NH3 IN BC EFFLUENT 2.65 PROPYLENE CONVERSION mole % 99.196 98.415

METHANOL CONVERSION mole % 86.517

PRODUCT RESULTS and RESULTS :

AN MAKE gma/hr 54223 54.047

HCN MAKE gma/hr 7.187 9.471

RATIO HCN /AN gms HCN/gm AN 0.133 0.175

NH3 Breakthrough gms/hr 1.250 0.028

NH3 Reduction gms/hr 1.222

TABLE 1

Example XVII

CATALYST: ZZE

REACTOR CONDITIONS :

REACTOR TEMP de C 462 461 461 460

REACTOR PRESS alms 2.01 2.01 2.01 2.01

METHANOL INJ POINT cms 0.00 0.00 0.00 0.00

ΛT % of CATALYST ABOVE the MeOH INJECTION PT. % 100.00 100.00 100.00

CATALYST CHARGE gms 400 400 400 400

REACTOR FEEDS :

NH3 EED MOUHR 1.426 1.652 1.702 1.717

C3H6 FEED MOUHR 1.299 1.299 1299 1.299

AIR FEED MOUHR 14.25 16.509 16.76 16.766

N2 FEED (w/MeOH) MOUHR 0274 0.374 0.374 0.374

METHANOL FEED MOUHR 0.503 0.503 0.503

NH3/C3H6 FEED RATIO 1.098 1272 1.310 1.322

AIR/C3H6 FEED RATIO 10.971 12.710 12.904 12.908

MeOH/C3H6 FEED RATIO 0.387 0.387 0.387

EFFLUENT CONDITIONS :

MOLE % NH3 in EFFLUENT 0.451 0.266 0.387 0.437 MOLE % 02 In EFFLUENT 3202 2.955 3.225 3.153 MOLES METHANOL OUT 0.006 0.006 0.006 MOLES MeOH FEED /MOLE NH3 IN BC EFFLUENT 6.12 6.12 6.12 PROPYLENE CONVERSION mole % 99.084 96.848 96.813 96.943

METHANOL CONVERSION mole % 98.900 98.889 98.888

PRODUCT RESULTS and RESULTS :

AN MAKE gma/hr 55.639 54.078 54.626 54.585

HCN MAKE gma/hr 6.943 15.262 15.625 15.629

RATIO HCN /AN gms HCN/g AN 0.125 0.282 0286 0.286

NH3 Breakthrough gms/hr 1.39B 0.978 1.444 1.632

NH3 Reduction gms/hr 0.420 -0.045 -0.014