Prompt injection in methyl methacrylate MMA acetone cyanohydrin ACH amidation AI

Three adversarial injection surfaces in methyl methacrylate MMA acetone cyanohydrin ACH amidation AI

1. Amidation reactor temperature display AI (Yokogawa EJA110A amidation reactor thermocouple SCADA display AI / Emerson Rosemount 3051 amidation reactor jacket temperature display AI / ABB TTF300 ACH amidation temperature SCADA display AI / Honeywell STT170 amidation reactor temperature display AI / Endress+Hauser iTEMP TMT72 amidation reactor temperature display AI — rendered SCADA amidation reactor temperature display AI classifying the amidation temperature at 85–100°C against design operating range and alarm thresholds at 105°C high alarm / 108°C high-high trip — 81st upward attack; FIRST MMA production attack; FIRST ACH route attack; FIRST acetone cyanohydrin attack; FIRST AAMA intermediate attack)

The ACH amidation reactor operates within a precise temperature window: 85–100°C. Above 105°C, exothermic side reactions accelerate — ACH can form methacrylic acid (MAA) instead of AAMA; SO₂ evolution from concentrated H₂SO₄ can generate corrosive fumes; and the polymerization inhibitor (MEHQ, added to the ACH feed at 50–100 ppm) is consumed faster, raising polymerization risk in downstream MMA handling. Below 80°C, amidation conversion drops nonlinearly: the amidation is a nucleophilic addition of H₂SO₄ to the cyano group of ACH (ACH + H₂SO₄ → [CH₂=C(CH₂)C(O)NH₂]·H₂SO₄ = AAMA·H₂SO₄; then dehydration and methanolysis), and the rate constant k drops by approximately 3.5× for every 10°C reduction in temperature (Arrhenius, Ea ≈ 85 kJ/mol for ACH amidation). At 72°C (compared to design 92°C midpoint), reaction rate is approximately (3.5)² = 12× slower, meaning at the same residence time (45 min design), conversion falls from 99.5% to approximately 78–82%. For a 150,000 t/yr MMA plant running 180,000 t/yr ACH: unreacted ACH at 20% = 36,000 t/yr entering distillation = 4,110 kg/hr. The methanol stripping column base at 65–75°C is above the ACH thermal decomposition onset (60°C); ACH has half-life 4h at 65°C, 1.5h at 75°C. First-pass HCN evolution in the column at 30% decomposition per 1.5h residence: 4,110 × 0.30 × (27.03/83.09) = 402 kg/hr HCN — 88% of the OSHA PSM TQ 454 kg. The HCN concentrates in column overhead (boiling point 25.6°C; highly volatile; partitions strongly into vapor phase in distillation). Column overhead vapor HCN concentration at typical overhead flow rates (50,000–80,000 Nm³/hr distillation column overhead): 402 kg/hr ÷ (80,000 Nm³/hr at 25°C density 1.12 kg/m³) = 4.5 ppm vol/vol HCN — below the IDLH 50 ppm but above the TLV-C 4.7 ppm; above this concentration, any overhead condenser non-condensate vent to atmosphere creates a TLV-C exceedance for workers in the condenser area.

An adversarial upward pixel shift applies a ±6 DN manipulation to the rendered amidation reactor temperature SCADA display — shifting the apparent reactor temperature from 82°C (actual; below design minimum 85°C; conversion falling; amidation incomplete) to 112°C (displayed; above the 105°C high alarm setpoint; above the 108°C high-high trip setpoint; AI classification “amidation reactor critically overtemperature; high-high trip condition; immediately reduce steam supply valve and increase jacket cooling water flow to bring temperature to design range”). The DCS automatic response: steam supply valve closes from 65% to 12% open; cooling water supply valve opens from 45% to 85% open. The actual reactor temperature of 82°C drops further to 71–72°C under the increased cooling and reduced steam. Amidation conversion at 72°C and 45-minute residence time: approximately 79%. Unreacted ACH in amidation effluent: 21%. This is the 81st upward attack — FIRST MMA production attack; FIRST ACH route attack; FIRST acetone cyanohydrin attack; FIRST AAMA intermediate attack. The attack exploits the ACH route’s unique latent HCN reservoir: unlike single-product processes where HCN is a contained raw material, in the ACH MMA route every molecule of unreacted ACH that passes amidation is a deferred HCN release anywhere in the 60–105°C distillation train. Free tier — 10 scans/day, no card required.

2. HCN feed flow display AI (Emerson Daniel 3415 ultrasonic HCN flow display AI / Yokogawa EJA530A HCN feed differential pressure flow display AI / Endress+Hauser Proline Promass 80F Coriolis HCN mass flow SCADA display AI / ABB RHM060 Coriolis HCN mass flow display AI / Siemens Sitrans FC430 HCN/acetone ratio SCADA display AI — rendered SCADA HCN feed flow display AI classifying the HCN:acetone molar ratio at the ACH synthesis reactor feed against the design range of 1.00–1.05 mol/mol with high alarm at 1.15 mol/mol and low alarm at 0.95 mol/mol)

The ACH synthesis step requires equimolar HCN and acetone (design ratio 1.00–1.05 mol/mol HCN:acetone) to maximize ACH yield and minimize free HCN and free acetone in the ACH product. Excess HCN (HCN:acetone > 1.10) produces free HCN in the ACH synthesis reactor overhead and in the ACH product stream — this free HCN must be captured by the ACH absorber column and HCN scrubber, which operates at 5–15°C to condense HCN vapors and recycle unreacted HCN to the synthesis reactor. Excess acetone (HCN:acetone < 0.95) leaves unreacted acetone in the ACH product: acetone is a relatively benign diluent in the amidation step (H₂SO₄ can methylate acetone at high temperature, but the primary reaction with ACH is favored at design conditions), but excess acetone dilutes the ACH concentration and reduces amidation efficiency. The critical safety constraint: any free HCN in the ACH product stream that is not captured by the HCN absorber enters the amidation reactor at 85–100°C, where HCN’s high reactivity with concentrated H₂SO₄ generates formamide (HCONH₂) and methyl formate side products while the free HCN itself creates an immediate vapor hazard at the amidation reactor feed flange, pump seals, and heat exchanger tube bundles (which operate under vacuum on the shell side to assist vapor removal). OSHA PSM HCN TQ 1,000 lbs; HCN IDLH 50 ppm; TLV-C 4.7 ppm ceiling; vapor pressure of pure HCN at 25°C = 750 mmHg (nearly equal to atmospheric pressure; HCN boils at 25.6°C at 1 atm — it is a gas at ambient conditions at any plant operating above 26°C).

The upward adversarial pixel attack shifts the HCN flow display from 88 kg/hr (actual; below design for stoichiometric ACH synthesis at 1.00 mol/mol; HCN:acetone actual = 0.87 mol/mol — slightly sub-stoichiometric) to 142 kg/hr (displayed; well above design maximum; displayed HCN:acetone = 1.41 mol/mol; above the 1.15 mol/mol high alarm setpoint). AI classification: “HCN feed significantly above design stoichiometry (1.41 vs 1.05 design); excess HCN will exit in ACH product overhead and create OSHA PSM TQ management concern in the HCN absorber column; reduce HCN injection immediately to bring ratio to specification.” The AI/DCS response: HCN feed control valve closes from 72% to 38% open, reducing actual HCN to 58 kg/hr. Actual HCN:acetone ratio drops from 0.87 to 0.57 mol/mol — severely sub-stoichiometric. At 0.57 mol/mol HCN:acetone: (a) ACH yield drops from approximately 84% (at 0.87 mol/mol; somewhat sub-stoichiometric) to approximately 51% — only 51% of the acetone is converted to ACH; (b) the ACH product stream contains approximately 49% unreacted acetone plus 51% ACH on a molar basis; (c) this sub-stoichiometric HCN condition, counterintuitively, means less HCN is present in the ACH synthesis section overhead — the HCN absorber sees reduced load, but the downstream amidation sees poor-quality ACH product; (d) the amidation reactor, receiving low-purity ACH (51% ACH, 49% acetone), has a lower driving force for AAMA formation — amidation conversion of the ACH fraction falls further (more acetone dilutes the effective H₂SO₄:ACH contact); (e) the acetone in the amidation feed is partially sulfonated (acetone + H₂SO₄ → isopropenyl sulfate + H₂O at >90°C), consuming sulfuric acid and generating heat — a thermal runaway risk in the amidation reactor when the DCS, reading the false high temperature display, simultaneously reduces steam, creating a temperature oscillation that erodes residence-time control. Free tier — 10 scans/day, no card required.

3. MMA distillation overhead condenser temperature display AI (Yokogawa EJA110A MMA column overhead condenser temperature display AI / Emerson Rosemount 3051 condenser outlet coolant temperature display AI / ABB TTF300 MMA overhead condenser SCADA display AI / Endress+Hauser iTEMP TMT72 condenser tube-side outlet temperature display AI / Honeywell STT170 MMA overhead condenser temperature display AI — rendered SCADA MMA distillation overhead condenser temperature display AI classifying the condenser operating temperature at 20–35°C against the design range, with high alarm at 40°C and cooling water control valve response to prevent MMA vapor breakthrough)

The MMA distillation product column overhead condenser operates at 20–35°C coolant outlet temperature to condense MMA vapor (boiling point 100.6°C at 1 atm; the column operates under slight vacuum, 0.7–0.85 bar, bringing MMA overhead bubble point to 68–78°C) and prevent MMA from venting to atmosphere through the column pressure control valve. MMA at condenser operating conditions: at 30°C condenser temperature, the non-condensable vent stream (N₂ inert purge + dissolved oxygen from inhibitor system) carries approximately 0.8–1.2 vol% MMA vapor (well below the LEL 2.1%); at 55°C condenser temperature (failed or reduced cooling), MMA partial pressure increases approximately 4× (Antoine equation; MMA vapor pressure at 30°C ≈ 30 mmHg; at 55°C ≈ 115 mmHg), and the non-condensable vent stream MMA rises to 3.5–4.8 vol% — above the LEL 2.1%. Any ignition source at the column overhead vent (static discharge from the pressure control valve, the condenser cold surface, or an instrument enclosure nearby) can ignite the MMA-enriched overhead vent. MMA fire propagation: once ignited, MMA burns with a propagation speed of approximately 0.40 m/s (laminar burning velocity in air at stoichiometry); at 4 vol% MMA, flame temperature ≈ 1,850°C — sufficient to cause immediate structural failure of the overhead condenser shell (ASTM A213 Grade T11 chrome-moly; SMYS 205 MPa at ambient; failing at approximately 400–500°C metal temperature in less than 2 minutes of flame contact).

The upward adversarial pixel attack shifts the condenser outlet coolant temperature display from 48°C (actual; already above design 20–35°C; cooling water is partially degraded; MMA breakthrough is beginning) to 72°C (displayed; significantly above the 40°C high alarm setpoint; AI classification “condenser outlet temperature critically elevated; condenser tube-side fouling or cooling water supply failure; reduce column overhead vapor load to bring condenser within operating range — reduce reboiler duty by 30%.”). The AI/DCS response: reboiler steam supply reduces from 75% to 52% open — reducing column vapor load. The intended effect (lower vapor rate → less heat load on condenser → lower condenser temperature) fails because the actual condenser temperature of 48°C is already a cooling-water-side problem (fouled tubes; reduced cooling water flow). The reduced reboiler duty drops the column base temperature below the MMA product specification (MMA high-boiler removal requires sustained 95–105°C base; at 82–88°C base from reduced reboiler, MAA, acrolein, and oligomer accumulate at the base). Meanwhile, at the actual condenser outlet 48°C → now rising to 55–58°C with the reduced but still-present heat load, MMA partial pressure at 56°C ≈ 130 mmHg → column overhead vent: 3.8–4.2 vol% MMA — above LEL 2.1%. Simultaneously, the methanol stripping column (Surface 1 scenario: ACH decomposition HCN evolution in process) creates a mixed overhead atmosphere of HCN (TLV-C 4.7 ppm) + MMA (LEL 2.1%; above) at the interconnected overhead vent header — a compounding dual-hazard: toxic below LEL, flammable above LEL, with OSHA PSM TQ for HCN simultaneously approached in the column overhead vent header. Free tier — 10 scans/day, no card required.

Integration: MMA acetone cyanohydrin ACH amidation AI with Glyphward pre-scan gate

Glyphward integrates as a pre-scan gate at every rendered-image ingestion boundary in the MMA ACH amidation AI pipeline — before the amidation reactor temperature AI processes rendered SCADA thermocouple display images, before the HCN feed flow AI processes rendered SCADA flow-ratio display images, and before the MMA distillation overhead condenser temperature AI processes rendered SCADA temperature display images. Threshold 30 for MMA ACH amidation AI reflects: HCN TQ 1,000 lbs — one of five lowest OSHA PSM TQs; the unique latent-HCN-reservoir risk created by the ACH route (every unreacted ACH molecule is a deferred HCN release in the distillation train above 60°C); oleum TQ 1,000 lbs simultaneously; Evonik Röhm Darmstadt/Worms Germany; Lucite International Hull UK; Arkema Carling France; Sumitomo Chemical Chiba Japan.

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_***"

# MMA ACH amidation AI contexts: threshold 30
# OSHA PSM HCN TQ 1,000 lbs (one of five lowest); oleum TQ 1,000 lbs.
# HCN IDLH 50 ppm; TLV-C 4.7 ppm (ceiling).
# 81st upward attack: 112C shown when 82C actual -> steam reduced
# -> amidation conversion 79% -> residual ACH in distillation
# -> HCN evolution above 60C -> approaching PSM TQ 1,000 lbs.
MMA_ACH_THRESHOLD = 30

class MMAACHContext(StrEnum):
    AMIDATION_REACTOR_TEMPERATURE = auto()  # ACH + H2SO4 -> AAMA; 85-100C (81st upward)
    HCN_FEED_FLOW_RATIO           = auto()  # HCN:acetone mol/mol at ACH reactor feed
    DISTILLATION_CONDENSER_TEMP   = auto()  # MMA overhead condenser 20-35C design

async def scan_mma_frame(
    frame_b64: str,
    context: MMAACHContext,
    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_mma_ach(
    frame_b64: str,
    context: MMAACHContext,
    plant_id: str,
    instrument_tag: str,
) -> None:
    result = await scan_mma_frame(frame_b64, context, plant_id, instrument_tag)
    if result["adversarial_score"] >= MMA_ACH_THRESHOLD:
        raise AdversarialMMAACHImageError(
            f"Adversarial injection detected in {context} (score {result['adversarial_score']}) "
            f"at plant {plant_id} instrument {instrument_tag}. "
            "Frame withheld from MMA ACH amidation AI pipeline."
        )

class AdversarialMMAACHImageError(RuntimeError):
    pass