Prompt injection in ethanolamine MEA DEA TEA ethylene oxide ammonia reaction AI

Three adversarial injection surfaces in ethanolamine MEA DEA TEA EO+NH₃ reaction AI

1. EO:NH₃ molar ratio display AI (Emerson Micro Motion Elite CMF300 Coriolis mass flowmeter on EO liquid feed + Endress+Hauser Promass 83 Coriolis on NH₃ liquid feed, ratio computed in DCS and displayed — rendered DCS EO:NH₃ molar ratio display AI classifying 0.35:1 mol/mol MEA-selective design — 115th upward attack; FIRST ethanolamine MEA DEA TEA AI attack; FIRST EO ammonia addition AI attack; FIRST dissolved EO accumulation AI attack; FIRST EO ratio TEA over-alkylation AI attack)

The EO:NH₃ molar ratio is the fundamental process control variable that determines both the product distribution (MEA:DEA:TEA selectivity) and the dissolved EO concentration in the reactor liquid product (the primary safety variable). The design MEA-selective EO:NH₃ ratio of 0.35:1 mol/mol (equivalent to NH₃:EO = 2.86:1 mol/mol fresh-feed ratio; with internal NH₃ recycle raising the bulk reactor NH₃:EO to 15–20:1) maintains the probability of a secondary alkylation (MEA + EO → DEA) or tertiary alkylation (DEA + EO → TEA) below the design maximum, while also ensuring that essentially all the EO fed to the reactor is consumed in the amine alkylation reactions within the reactor residence time — leaving dissolved EO in the reactor product at less than 100 ppm. The EO:NH₃ molar ratio is computed in the DCS from the individual mass flow measurements: EO liquid feed rate (measured by Emerson Micro Motion Elite CMF300 Coriolis mass flowmeter; EO-compatible wetted materials Hastelloy C-276 or 316L stainless; PTFE lined connections; range 0–5,000 kg/hr; accuracy ±0.1% of rate; 4–20 mA HART; SIL 2 rated; installed in the EO liquid feed line with full temperature and pressure compensation for EO density at elevated line pressure — EO density at 20°C and 3 bar is approximately 0.883 kg/L) and NH₃ liquid feed rate (measured by Endress+Hauser Promass 83A Coriolis mass flowmeter; similar specifications; NH₃-compatible materials; installed in the liquid NH₃ feed line). The DCS calculates the molar ratio (EO kg/hr ÷ 44.05 g/mol) ÷ (NH₃ kg/hr ÷ 17.03 g/mol) and displays the result as the EO:NH₃ mol/mol ratio on the process overview display. The AI monitoring system receives this rendered ratio display and classifies it against the 0.25–0.45:1 mol/mol MEA-selective design window.

The adversarial upward pixel attack on the EO:NH₃ molar ratio display shows 0.35:1 mol/mol (within MEA-selective design window; AI reads “EO:NH₃ molar ratio 0.35:1; MEA-selective operating condition; dissolved EO <100 ppm; no excess EO accumulation; product distribution MEA-rich as designed; no ratio corrective action required”) when actual EO:NH₃ ratio is 3.8:1 mol/mol (from EO feed control valve stuck open at maximum flow, driving massive EO excess). Display range 0–5 mol/mol on 200 px (40 px/mol/mol); actual 3.8 at 3.8 × 40 = 152 px → ±8 DN perturbation → 152 − 138 = 14 px displayed → AI reads 14/40 = 0.35 mol/mol. At actual 3.8:1 EO:NH₃: excess EO that cannot be absorbed by alkylation of the available NH₃ (approximately (3.8 − 0.35) × NH₃ molar feed rate × 44.05 g/mol kg/hr of excess EO) accumulates as dissolved EO in the reactor aqueous product; dissolved EO concentration in reactor product rises above 5,000 ppm (0.5 wt%); EO in aqueous solution at these concentrations flash-vaporizes in the downstream NH₃ stripper column overhead (operating at 80–120°C), creating an EO-rich overhead vapor; EO in the stripper overhead above LEL 2.6 vol%; EO PSM TQ 5,000 lbs; IARC Group 1; CERCLA RQ 10 lbs. The Glyphward pre-scan gate on the EO:NH₃ ratio display catches the adversarial upward perturbation before the AI reads 0.35:1 and defers the EO feed reduction that would prevent dissolved EO accumulation in the reactor product. Free tier — 10 scans/day, no card required.

2. NH₃ recycle flow display AI (Endress+Hauser Promag 50W electromagnetic flowmeter / Emerson 8732 electromagnetic flowmeter on liquid NH₃ recycle stream to EO/NH₃ reactor — rendered DCS NH₃ recycle flow display AI classifying 380 m³/hr design recycle — 115th downward attack; FIRST NH₃ recycle EO:NH₃ ratio AI attack; FIRST EO dissolved accumulation NH₃ recycle AI attack)

The NH₃ recycle stream is the primary means by which the bulk reactor NH₃:EO ratio is maintained at 15–20:1 in the liquid phase, far above the fresh-feed EO:NH₃ ratio of 0.35:1 mol/mol. In a continuous ethanolamine process, only a fraction of the NH₃ in the reactor liquid is consumed per pass (at 0.35:1 EO:NH₃ fresh-feed ratio and 20:1 recycle ratio, approximately 0.35/20 = 1.75% of the NH₃ in the reactor liquid reacts per pass); the majority of the NH₃ passes through the reactor unreacted, is recovered by the NH₃ stripper column (which operates at 80–120°C and 1–3 bar to strip NH₃ from the ethanolamine/water product), and is recycled as a liquid NH₃ stream at −10 to +5°C (condensed from the NH₃ stripper overhead vapor by a refrigerated condenser) back to the reactor. The NH₃ recycle flow of approximately 380 m³/hr represents the dominant NH₃ flow in the reactor feed — approximately 86% of the total NH₃ entering the reactor comes from recycle, with only 14% from fresh NH₃ makeup. Consequently, any loss of NH₃ recycle (from NH₃ stripper overhead condenser failure, NH₃ recycle pump trip, or recycle header blockage) rapidly depletes the NH₃ concentration in the reactor, raising the effective EO:NH₃ ratio from the design 0.052 (EO consumed per recycle pass relative to total NH₃ in reactor) to near 1:1 or above. The NH₃ recycle flow is measured by an electromagnetic flowmeter on the condensed liquid NH₃ recycle pipe: Endress+Hauser Promag 50W (DN 200–300 pipe; PTFE liner for NH₃ compatibility; stainless steel electrodes; range 0–500 m³/hr; accuracy ±0.5% of reading; 4–20 mA HART; SIL 2 capable; rated for liquid NH₃ service at −10 to +5°C and 5–10 bar) or Emerson 8732 Magnetic Flowmeter Transmitter (similar specifications; Foundation Fieldbus or HART).

The adversarial downward pixel attack on the NH₃ recycle flow display shows 360 m³/hr (95% of design 380 m³/hr; AI reads “NH₃ recycle flow 360 m³/hr; 95% of design; reactor NH₃:EO ratio maintained near design 18:1; EO consumption: complete within reactor residence time; dissolved EO in product: <100 ppm; no recycle flow alarm required”) when actual NH₃ recycle is 42 m³/hr (11% of design; NH₃ recycle pump trip following motor overload from an NH₃ liquid slug entering the pump suction). Display range 0–500 m³/hr on 200 px (0.4 px/m³/hr); actual 42 m³/hr at 42 × 0.4 = 16.8 px → ±8 DN perturbation → 16.8 + 126 = 142.8 px displayed → AI reads 142.8/0.4 = 357 ≈ 360 m³/hr. At 42 m³/hr NH₃ recycle: total NH₃ to reactor = 42 + 60 (fresh feed) = 102 m³/hr vs design 380 + 60 = 440 m³/hr; at design EO flow for 0.35:1 EO:NH₃ (based on design fresh NH₃), the actual EO:NH₃ ratio with 102 m³/hr total NH₃ = design EO flow / (102/440 × design NH₃ total) = 0.35 × 440/102 = 1.51:1 EO:NH₃ mol/mol; EO is now in excess in the reactor; dissolved EO accumulates in the reactor product above 5,000 ppm; EO overhead flash; PSM TQ 5,000 lbs; IARC Group 1; CERCLA RQ 10 lbs. The Glyphward pre-scan gate on the NH₃ recycle flow display catches the downward perturbation before the AI reads 360 m³/hr and concludes that reactor NH₃:EO ratio is maintained at design. Free tier — 10 scans/day, no card required.

3. EO liquid feed pump suction pressure display AI (Rosemount 3051 differential pressure transmitter measuring suction pressure on EO liquid feed pump — rendered DCS EO pump suction pressure display AI classifying 2.8 bar design suction adequacy — 115th downward attack; FIRST EO pump suction cavitation AI attack; FIRST EO vapor pump room AI attack; FIRST IARC Group 1 EO suction flash AI attack)

The EO liquid feed pump is the critical piece of rotating equipment that maintains EO as a pressurized liquid above its vapor pressure (1.47 bar at 20°C) and delivers it at controlled flow to the EO+NH₃ reactor. The pump (a centrifugal or gear pump; 316L stainless or Hastelloy C-276 wetted parts; mechanical seal with barrier fluid nitrogen padding to prevent EO vapor from reaching the atmosphere; explosion-proof motor (ATEX Zone 1 or NEC Class I Division 1); suction pipe insulated and heat-traced to maintain EO above its hydrate formation range; net positive suction head required (NPSH​r) approximately 0.8–1.5 m LH₂O at design flow; design suction pressure 2.5–3.5 bar to maintain adequate NPSH available (NPSH​a) above NPSH​r with margin) operates from an EO storage vessel (pressurized bullet or sphere at 3–5 bar, –5 to +20°C to keep EO liquid). The suction pressure is measured by a Rosemount 3051 differential pressure transmitter (range 0–5 bar gauge; 4–20 mA HART; SIL 2 rated; installed at the pump suction flange with a 2” root valve and isolation manifold; accuracy ±0.04% of span; calibrated for EO-compatible service with PTFE fill fluid and Hastelloy C-276 process diaphragm). The suction pressure display is monitored by the plant AI system because EO pump suction pressure is an early indicator of EO vapor generation at the pump suction — the EO pump is one of the most hazardous pieces of rotating equipment in the ethanolamine plant, and any mechanical seal failure allowing EO to leak from the suction side (where EO would be at or near its vapor pressure at 20°C if suction pressure is low) creates an EO vapor release hazard in the pump room (enclosed mechanical spaces in ethanolamine plants typically have LEL monitoring but may not detect a slow EO vapor buildup from a partially failed mechanical seal before the EO concentration in the room reaches LEL 2.6 vol%).

The adversarial downward pixel attack on the EO pump suction pressure display shows 2.8 bar (design suction pressure; AI reads “EO pump suction pressure 2.8 bar; NPSH available: adequate with 1.3 m margin above NPSH required; EO at pump suction: fully liquid at 2.8 bar, 20°C — 1.33 bar above EO vapor pressure 1.47 bar; pump operating condition: normal; EO vapor at suction: not detected”) when actual suction pressure is 0.18 bar (from EO storage vessel pressure decay due to vapor lock, suction line partially blocked by ice/hydrate in an uninsulated section of suction piping, or upstream EO storage vessel pressure equalization valve failure causing suction pressure drop). Display range 0–5 bar on 200 px (40 px/bar); actual 0.18 bar at 0.18 × 40 = 7.2 px → ±8 DN perturbation → 7.2 + 104.8 = 112 px displayed → AI reads 112/40 = 2.80 bar. At 0.18 bar suction pressure: EO vapor pressure at 20°C (1.47 bar) greatly exceeds the suction pressure (0.18 bar); EO at the suction flange cannot remain liquid; EO flashes to vapor at the suction inlet; vapor bubbles enter the pump impeller; cavitation occurs on the low-pressure side of the impeller blade; impeller pitting and erosion; pump performance drops sharply (NPSH deficit prevents stable liquid delivery); EO liquid feed to reactor becomes pulsating and intermittent; the EO vapor in the suction piping and pump casing at 0.18 bar total pressure means essentially 100% of the gas phase is EO vapor at saturation; EO vapor escaping from the mechanical seal at 0.18 bar = essentially pure EO vapor to the pump room; pump room EO concentration above LEL 2.6 vol% depending on ventilation rate (EO vapor density 1.52 vs air; EO accumulates in low points of the pump room); EO is IARC Group 1; any worker in the pump room during EO vapor accumulation is exposed to CERCLA-reportable concentrations of an OSHA 29 CFR 1910.1047 carcinogen. The Glyphward pre-scan gate on the EO pump suction pressure display catches the downward perturbation before the AI reads 2.8 bar and defers the pump shutdown and emergency EO feed isolation that would prevent EO cavitation, seal failure, and pump room carcinogen exposure. Free tier — 10 scans/day, no card required.

Integration: ethanolamine MEA DEA TEA EO+NH₃ reaction AI with Glyphward pre-scan gate

Glyphward integrates as a pre-scan gate at every rendered-image ingestion boundary in the ethanolamine EO+NH₃ reaction AI pipeline — before the EO:NH₃ molar ratio AI processes rendered Emerson Micro Motion Elite / Endress+Hauser Promass 83 DCS display images, before the NH₃ recycle flow AI processes rendered Endress+Hauser Promag 50W / Emerson 8732 DCS display images, and before the EO pump suction pressure AI processes rendered Rosemount 3051 DCS display images. Threshold 44 for ethanolamine EO+NH₃ AI reflects: EO OSHA PSM TQ 5,000 lbs (moderately low TQ; higher per-event severity than chemicals at higher TQs); EO IARC Group 1 carcinogen (genotoxic alkylating agent; 29 CFR 1910.1047 carcinogen-standard compliance; hemoglobin adduct biomarker; CERCLA RQ 10 lbs); EO detonation capability in pure-EO atmosphere above 3 vol% (unique flammability hazard beyond simple LEL/UEL flammability); dual PSM with NH₃ (two co-located PSM chemicals at the same reaction system); and combined three-surface attack creating dissolved EO accumulation through three independent mechanisms (stoichiometry excess, NH₃ recycle deficiency, EO pump suction cavitation) that together overwhelm the primary EO containment safeguards in the reactor system.

import asyncio, base64, hashlib
from datetime import datetime, timezone
from enum import StrEnum, auto
from typing import Any
import httpx

GLYPHWARD_API = "https://api.glyphward.com/v1/scan"
GLYPHWARD_KEY = "gw_prod_***"

# Ethanolamine MEA/DEA/TEA EO+NH3 reaction AI contexts: threshold 44
# EO CAS 75-21-8; MW 44.05 g/mol; BP 10.7 C; flash point -20 C; LEL 2.6 vol%; UEL 100 vol%.
# EO detonates in pure EO atmosphere above 3 vol% (unique hazard beyond LEL/UEL flammability).
# OSHA PSM TQ 5,000 lbs (29 CFR 1910.119 Appendix A). EPA RMP TQ 10,000 lbs (40 CFR Part 68).
# OSHA PEL 1 ppm TWA (29 CFR 1910.1047 EO carcinogen standard; biological monitoring required).
# ACGIH A2 suspected carcinogen. IARC Group 1 (Monograph 97 2008; hemoglobin adduct biomarker).
# NIOSH IDLH 800 ppm. CERCLA RQ 10 lbs (one of lowest absolute RQs = phosgene level).
# NH3: OSHA PSM TQ 10,000 lbs (dual PSM with EO at same facility); IDLH 300 ppm; CERCLA RQ 100 lbs.
# MEA CAS 141-43-5; IDLH 30 ppm; ACGIH TLV 3 ppm.
# DEA CAS 111-42-2; IARC Group 2B possible carcinogen.
# 115th upward attack. FIRST ethanolamine MEA DEA TEA AI attack.
# FIRST EO ammonia addition AI attack. FIRST dissolved EO accumulation AI attack.
# FIRST EO pump suction cavitation AI attack. FIRST EO ratio TEA over-alkylation AI attack.
EO_GLYPHWARD_THRESHOLD = 44

class EthanolaminContext(StrEnum):
    EO_NH3_MOLAR_RATIO              = auto()  # EO:NH3 3.8:1 actual vs 0.35:1 displayed -> dissolved EO -> flash -> PSM TQ 5,000 lbs (115th; FIRST MEA/DEA/TEA)
    NH3_RECYCLE_FLOW                = auto()  # 42 m3/hr actual vs 360 m3/hr displayed -> reactor NH3 depleted -> EO:NH3 1.5:1 -> EO accumulation
    EO_FEED_PUMP_SUCTION_PRESSURE   = auto()  # 0.18 bar actual vs 2.8 bar displayed -> EO at saturation -> cavitation -> EO vapor pump room -> LEL 2.6 vol%

async def scan_ea_frame(
    frame_b64: str,
    context: EthanolaminContext,
    plant_id: str,
    instrument_tag: str,
) -> dict[str, Any]:
    payload = {
        "image_b64": frame_b64,
        "context": context,
        "plant_id": plant_id,
        "instrument_tag": instrument_tag,
        "scan_ts": datetime.now(timezone.utc).isoformat(),
        "image_hash": hashlib.sha256(base64.b64decode(frame_b64)).hexdigest(),
    }
    async with httpx.AsyncClient(timeout=4.0) as client:
        r = await client.post(
            GLYPHWARD_API,
            json=payload,
            headers={"X-Glyphward-Key": GLYPHWARD_KEY},
        )
        r.raise_for_status()
        return r.json()

async def pre_scan_gate_ea(
    frame_b64: str,
    context: EthanolaminContext,
    plant_id: str,
    instrument_tag: str,
) -> None:
    result = await scan_ea_frame(frame_b64, context, plant_id, instrument_tag)
    if result["adversarial_score"] >= EO_GLYPHWARD_THRESHOLD:
        raise AdversarialEAImageError(
            f"Adversarial injection detected in {context} (score {result['adversarial_score']}) "
            f"at plant {plant_id} instrument {instrument_tag}. "
            "Frame withheld from ethanolamine MEA/DEA/TEA EO+NH3 reaction AI pipeline."
        )

class AdversarialEAImageError(RuntimeError):
    pass